Gasification of carbonaceous materials and gas to liquid processes

ABSTRACT

Herein disclosed is a method of reacting one or more components in a liquid medium to form an organic product that may include feeding a carbonaceous gas and a liquid medium to a high shear device; processing the gas and the liquid medium under shearing conditions in the high shear device, resulting in an emulsion comprising at least some of the carbonaceous gas dispersed in the liquid medium, wherein the dispersed carbonaceous gas comprises gas bubbles with a mean diameter of less than about 1 μm; and reacting the emulsion to produce the organic product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/844,728, filed Jul. 27, 2010, now U.S. Pat. No. 8,394,861, whichclaims the benefit under 35 U.S.C. §119(e) of U.S. Provisional PatentApplication No. 61/231,261, filed Aug. 4, 2009. This application is acontinuation-in-part of U.S. patent application Ser. No. 12/140,763,filed Jun. 17, 2008, now U.S. Pat. No. 8,026,403, which claims thebenefit under 35 U.S.C. §119(e) of U.S. Provisional Patent ApplicationNo. 60/946,444, filed Jun. 27, 2007, and U.S. Provisional PatentApplication No. 61/039,235, filed Mar. 25, 2008. This application isalso a continuation-in-part of U.S. patent application Ser. No.12/138,269, filed Jun. 12, 2008, now U.S. Pat. No. 8,133,925, whichclaims the benefit under 35 U.S.C. §119(e) of U.S. Provisional PatentApplication No. 60/946,468, filed Jun. 27, 2007. The disclosure of eachof the aforementioned applications is hereby incorporated herein byreference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable.

BACKGROUND OF THE INVENTION

1. Technical Field

The present invention generally relates to the production of syngas fromhydrocarbon sources such as coal peat, coke, methane, biogas, coker gasand other hydrocarbon sources. The present application also relates toconversion of light gases (such as carbon monoxide, carbon dioxide,methane, hydrogen, and/or water) into hydrocarbons and/or liquidoxygenates. The invention relates more particularly to apparatus andmethods for producing liquid oxygenates and/or hydrocarbons using highshear.

2. Background of the Invention

The effect of increasing carbon dioxide emission on global warming is amajor concern of scientists and governments due to its effect on theenvironment. The increased use of fossil fuels as a source of power andheat is the main reason for the increase in carbon dioxide emissions.The combustion of fossil fuels is an exothermic process where the energyreleased is typically used for heating and/or conversion to other formsof energy such as mechanical energy. Oxidation of hydrocarbons is alsocommon practice in chemical reactions such as oxidation of ethylene,Fischer Tropsch and other reactions. The resulting effluent fromcombustion of hydrocarbon depends on the make up of the hydrocarbon butis mainly carbon dioxide and water. Releasing large amounts of carbondioxide into the atmosphere is believed to be responsible for adverseeffects to the environment and there are efforts underway to reducecarbon dioxide emissions to help abate these negative effects.

A viable solution to the deleterious environmental effects of carbondioxide emissions should result in a net reduction of carbon dioxideemissions. Technologies to sequester carbon dioxide can consume largeamounts of energy, the energy, in many cases, derived from fossil fuels,and thus resulting in little or no net reduction in carbon dioxide, orworse yet a net increase in carbon dioxide production.

A process that allows recycling carbon dioxide to produce a valuableproduct such as fuel or chemical feedstock would be of great benefit inreducing the purported effects of carbon dioxide on global warming. Itwould be additionally beneficial to develop a process to convert carbondioxide into a liquid fuel that can be transported and/or used as afeedstock for refinery or petrochemical processes.

Methane is an important building block in organic reactions used inindustry as well as an important fuel source. The methane content ofnatural gas may vary within the range of from about 40 volume percent toabout 95 volume percent. Other constituents of natural gas may includeethane, propane, butanes, pentane (and heavier hydrocarbons), hydrogensulfide, carbon dioxide, helium and nitrogen. Natural gas in liquid formhas a density of 0.415 and a boiling point of minus 162° C. It istherefore not readily adaptable to transport as a liquid except formarine transport in very large tanks with a low surface to volume ratio.Large-scale use of natural gas often requires a sophisticated andextensive pipeline system. A significant portion of the known naturalgas reserves is associated with remote fields, to which access isdifficult. For many of these remote fields, pipelining to bring the gasto potential users is not economically feasible. Economicallytransporting methane from remote areas by converting the gas to a liquidhas long been sought in the industry.

Indirectly converting methane to methanol by steam-reforming to producesynthesis gas as a first step, followed by catalytic synthesis ofmethanol is a well-known process. Aside from the technical complexityand the high cost of this two-step, indirect synthesis, the methanolproduct has a limited market and the process thus does not appear tooffer a practical way to utilize natural gas from remote fields.

A process that provides an effective means for catalytically convertingmethanol to gasoline is described in U.S. Pat. No. 3,894,107 (Butter etal.). Although the market for gasoline is large relative to the marketfor methanol, and although this process was used in New Zealand, it iscomplex and its viability appears to be limited to situations in whichthe cost for supplying an alternative source of gasoline is high.Because of the high cost of producing gasoline from this process, it wasshut down.

Attempts to carry out the partial oxidation of methane to liquidcompounds (such as methanol or ethanol) in the gas phase have met withlimited success because of difficulties in controlling the free radicalprocesses that are involved. Since methanol is more reactive thanmethane, the undesirable formation of CO and CO₂ via secondarycombustion has been unavoidable. While a variety of catalysts, mostlymetal oxides, have been reported for the partial oxidation of methane tomethanol, the reaction has required high temperatures and the reportedmethanol yields based on methane have generally been less than 10%.

Other approaches for the conversion of methane to methanol have beenreported by Bjerrum, U.S. Pat. No. 6,380,444; Periana, U.S. Pat. No.5,233,113; and Chang, U.S. Pat. No. 4,543,434. The general reactionsystem used for these approaches utilize a small quantity of a radicalinitiator (acid) that will strip a hydrogen atom from methane, togenerate methyl radicals and a small quantity of acid. Some patents havedemonstrated that methane can be converted to methyl bisulfate in asingle-step using Group VIII noble metal catalyst (such as platinum orpalladium), and a strong inorganic acid such as sulfuric acid. Otherpatents describe processes which do not utilize catalyst in theconversion of methane to methanol (e.g., European Patent No. 1,558,353).Chlorine and other halogen containing acids have also been utilized in asimilar manner to convert methane to methanol and other liquids. Theseprocesses tend to encounter problems with corrosion at elevatedtemperatures, produce relatively low yields of methanol, and createunwanted byproduct.

U.S. Pat. No. 7,282,603 to Richards discloses anhydrous processing ofmethane into methane sulfonic acid, methanol and other compounds andprovides an overview of some of the past approaches to convertingmethane into methanol. The approach of Richards avoids the use orcreation of water, and utilizes a radical initiator compound such ashalogen gas or Marshall's acid to create methyl radicals.

Existing processes and production facilities for producing liquids frommethane are typically subject to various constraints such as mass flowand product yield limitations and plant size and energy consumptionrequirements.

Accordingly, in view of the art, there is a need for efficient andeconomical methods and systems for converting carbon dioxide and/or lowmolecular weight alkanes, in particular methane, into valuable productswhereby the emission of carbon dioxide into the environment may bereduced and/or a system and process whereby a light gas streamcomprising carbon dioxide and/or methane may be converted into a liquidproduct. The greenhouse gas problem is addressed by the herein disclosedsystem and process for the conversion of carbon dioxide to hydrocarbonsand/or oxygenates through the use of a high shear reactor. Such systemsand methods should permit increased selectivity and yield of liquidoxygenates and conversion of methane and/or carbon dioxide, whileallowing economically favorable conditions of operating temperature,pressure and/or reaction time.

SUMMARY

Herein disclosed is a method of producing synthesis gas fromcarbonaceous material, the method comprising: (a) providing a mixturecomprising carbonaceous material and a liquid medium; (b) subjecting themixture to high shear under gasification conditions whereby a highshear-treated stream comprising synthesis gas is produced; and (c)separating a product comprising synthesis gas from the highshear-treated stream. In an embodiment, (b) subjecting the mixture tohigh shear to produce a high shear-treated stream comprising synthesisgas comprises contacting the mixture with at least one gas or vaporselected from the group consisting of steam, hydrogen, air, oxygen, andassociated gas.

In an embodiment, the method further comprises contacting the mixturewith a catalyst that promotes the formation of synthesis gas. In anembodiment, the method further comprises recycling separated unreactedcarbonaceous material, separated liquid medium or both from (c) to (a).In an embodiment, the carbonaceous material comprises coke, coal, peat,natural gas, or a combination thereof. In some cases, the coal isselected from the group consisting of bituminous, anthracite, andlignite. In an embodiment, the carbonaceous material comprises powderedcoal or coalbed methane.

In an embodiment, the method further comprises utilizing at least aportion of the synthesis gas to produce a liquid product comprisingforming a dispersion of synthesis gas in a liquid phase. In anembodiment, utilizing at least a portion of the synthesis gas to producea liquid product comprises catalytically reacting the at least a portionof the synthesis gas to produce Fischer-Tropsch hydrocarbons. In anembodiment, the liquid product comprises liquid hydrocarbons andalcohols. In an embodiment, the liquid product comprises primarilyliquid hydrocarbons, primarily alcohols, or substantially equivalentamounts of alcohols and liquid hydrocarbons. In an embodiment, theliquid phase comprises one or more liquid hydrocarbon produced byFischer-Tropsch, one or more alcohol, or a combination thereof. In anembodiment, the method of forming a dispersion comprises introducing thesynthesis gas and liquid carrier into a high shear device comprising atleast one rotor and at least one stator and providing a tip speed of atleast about 23 m/sec, wherein the tip speed is defined as πDn, where Dis the diameter of the at least one rotor and n is the frequency ofrevolution. In an embodiment, the method further comprises introducingthe dispersion into a reactor comprising a fixed bed of catalyst or afluidized bed of catalyst. In an embodiment, a method of producingliquid product comprising alcohol from synthesis gas comprisesintroducing synthesis gas obtained via the method disclosed herein andliquid carrier into a high shear device comprising at least one rotorand at least one complementarily-shaped stator; and subjecting thecontents of the high shear device to a shear rate of at least 10,000s⁻¹, wherein the shear rate is defined as the tip speed divided by theshear gap, wherein the tip speed is defined as πDn, where D is thediameter of the at least one rotor and n is the frequency of revolution.

Herein also disclosed is a method for producing a liquid product. Themethod comprises forming a dispersion comprising gas bubbles dispersedin a liquid phase in a high shear device, wherein the average gas bubblediameter is less than about 1.5 μm; contacting the dispersion with amultifunctional catalyst to form the liquid product; and recovering theliquid product. In an embodiment, the liquid product is selected fromthe group consisting of C2+ hydrocarbons, C2+ oxygenates, andcombinations thereof. In an embodiment, the gas is selected from thegroup consisting of carbon dioxide, methane, ethane, propane, butane,pentane, methanol, and combinations thereof. In an embodiment, the gascomprises a hydrogen source or the liquid phase comprises a hydrogensource. In an embodiment, the gas comprises synthesis gas. In somecases, the synthesis gas is generated via natural gas reforming. In somecases, the synthesis gas is generated via solids gasification. In anembodiment, the solid is selected from the group consisting of coal,biomass, and bio-renewables.

In an embodiment, the multifunctional catalyst promotes Fischer-Tropschreactions. In an embodiment, the multifunctional catalyst promotesdehydrogenation reactions. In an embodiment, the multifunctionalcatalyst promotes alcohol forming reactions. In an embodiment, themultifunctional catalyst promotes at least two of the followingreactions: dehydrogenation, water dissociation, carbon dioxidedissociation, syngas reforming, and alcohol synthesis. In an embodiment,the high shear device comprises a catalytic surface.

Herein described is a system for producing a liquid product, comprisingat least one high shear mixing device comprising at least one inlet, atleast one outlet, at least one rotor and at least one stator separatedby a shear gap, wherein the shear gap is the minimum distance betweenthe at least one rotor and the at least stator, and wherein the highshear mixing device is capable of producing a tip speed of the at leastone rotor of greater than 22.9 m/s (4,500 ft/min); and a pump configuredfor delivering a fluid stream comprising liquid medium via the at leastone inlet to the high shear mixing device. In an embodiment, the systemfurther comprises a reactor comprising at least one inlet and at leastone outlet, wherein the at least one inlet of the reactor is fluidlyconnected to the at least one outlet of the high shear mixing device andthe at least one outlet of the reactor is configured for extracting theliquid product.

In an embodiment, the reactor is a Fischer-Tropsch reactor, a fixed-bedreactor, or a slurry reactor. In an embodiment, the reactor comprises amultifunctional catalyst. In an embodiment, the multifunctional catalystpromotes both Fischer-Tropsch reactions and alcohol forming reactions orboth dehydrogenation reactions and alcohol forming reactions. In anembodiment, the multifunctional catalyst promotes at least two of thefollowing reactions: dehydrogenation, water dissociation, carbon dioxidedissociation, syngas reforming, and alcohol synthesis. In an embodiment,the high shear mixing device of the system comprises a catalyticsurface.

Further described herein is a system for producing synthesis gas fromcarbonaceous material. The system comprises apparatus for providing amixture comprising carbonaceous material and a liquid medium; at leastone high shear device comprising at least one rotor and at least onecomplementarily-shaped stator and configured to subject the mixture tohigh shear and produce a high shear-treated stream comprising synthesisgas, wherein the at least one rotor is configured to provide a tip speedof at least about 23 m/sec, wherein the tip speed is defined as πDn,where D is the diameter of the at least one rotor and n is the frequencyof revolution; and a pump configured for delivering the mixture to theat least one high shear device. In an embodiment, the system furthercomprises a vessel coupled to the at least one high shear device, thevessel configured for receiving a high shear-treated stream from the atleast one high shear device. In an embodiment, the at least one rotor isseparated from the at least one stator by a shear gap in the range offrom in the range of from about 0.02 mm to about 5 mm, wherein the sheargap is the minimum distance between the at least one rotor and the atleast one stator. In an embodiment, the system further comprises a linefor introducing a dispersible gas or vapor into the mixture upstream ofthe at least one high shear device or into the at least one high sheardevice. In an embodiment, the system comprises more than one high sheardevice. In an embodiment, the at least one high shear device comprisesat least two generators, wherein each generator comprises a rotor and acomplementarily-shaped stator. In an embodiment, the system furthercomprises apparatus for the production of liquid hydrocarbons, alcoholsor a combination thereof wherein the apparatus for producing liquidhydrocarbons, alcohols or a combination thereof is fluidly connectedwith an outlet of the at least one high shear device.

Embodiments of the present disclosure are directed to a method ofreacting one or more components in a liquid medium to form an organicproduct that may include the steps of feeding a carbonaceous gas and aliquid medium to a high shear device; processing the gas and the liquidmedium under shearing conditions in the high shear device, resulting inan emulsion comprising at least some of the carbonaceous gas dispersedin the liquid medium, wherein the dispersed carbonaceous gas comprisesgas bubbles with a mean diameter of less than about 1 μm; and reactingthe emulsion to produce the organic product. In an embodiment, thecarbonaceous gas may include carbon monoxide and the hydrogen-basedliquid medium may include methanol.

The method may include feeding hydrogen to the high shear device, andthe organic product may comprise ethanol. The method may also includeutilizing a catalyst to promote the formation of the organic product. Insome embodiments, the catalyst may be a hydrogenation catalyst. In otherembodiments, the catalyst may be a carbonylation catalyst.

In some aspects, the high shear device produces a local pressure of atleast about 1034.2 MPa (150,000 psi) at the tip of a first rotordisposed therein. In other aspects, the organic product may includealkanes, olefins, aromatics, or combinations thereof. The high sheardevice may include a first rotor and a first stator configured with ashear gap therebetween. The shearing conditions may include a localizedtemperature at a tip of the first rotor of at least 500° C.

Other embodiments of the disclosure pertain to a method of producing aliquid product comprising an organic that may include the steps ofintroducing gas and liquid carrier into a high shear device comprisingat least one rotor and at least one complementarily-shaped stator; andshearing contents of the high shear device at a shear rate of at least10,000 s⁻¹, resulting in an emulsion comprising at least some of the gasdispersed in the liquid carrier, wherein the dispersed gas comprises gasbubbles with a mean diameter of less than about 1 μm; reacting theemulsion to produce the liquid product; and recovering the liquidproduct.

In some aspects, the liquid product may include C2+ hydrocarbons, C2+oxygenates, and combinations thereof. In other aspects, the gas may beselected from the group consisting of carbon dioxide, carbon monoxide,methane, ethane, propane, butane, pentane, methanol, and combinationsthereof. In an embodiment, the gas comprises a hydrogen source, and theorganic may be one of alkanes, olefins, aromatics, or combinationsthereof.

Yet other embodiments of the disclosure pertain to a system forproducing an organic that may include at least one high shear mixingdevice comprising a rotor and a stator separated by a shear gap; a pumpconfigured for delivering a fluid stream comprising liquid medium to thehigh shear mixing device; and a reactor comprising at least one inletand at least one outlet, wherein the at least one inlet of the reactoris fluidly connected to the high shear mixing device, and the reactor isconfigured for extracting the organic therefrom.

In some aspects, the reactor may be a Fischer-Tropsch reactor, afixed-bed reactor, or a slurry reactor. The reactor may include amultifunctional catalyst. In an embodiment, the multifunctional catalystmay promote at least two of the following reactions: dehydrogenation,water dissociation, carbon dioxide dissociation, syngas reforming, andalcohol synthesis.

In other aspects, the high shear mixing device comprises a catalyticsurface. In yet other aspects, the rotor may be separated from thestator by a shear gap in the range of from in about 0.02 mm to about 5mm.

Certain embodiments of an above-described method or system potentiallyprovide for more optimal time, temperature and pressure conditions thanare otherwise possible, and which potentially increase the rate of themultiphase process. Certain embodiments of the above-described methodsor systems potentially provide overall cost reduction by operating atlower temperature and/or pressure, providing increased product per unitof catalyst consumed, decreased reaction time, and/or reduced capitaland/or operating costs. These and other embodiments and potentialadvantages will be apparent in the following detailed description anddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more detailed description of the preferred embodiment of thepresent invention, reference will now be made to the accompanyingdrawings, wherein:

FIG. 1 is a schematic of a multiphase reaction system according to anembodiment of this disclosure comprising external high shear dispersing.

FIG. 2 is a longitudinal cross-section view of a multi-stage high sheardevice, as employed in an embodiment of the system.

FIG. 3 is a process flow diagram of a high shear Fischer-Tropsch systemfor conversion of synthesis gas to C2+ hydrocarbons according to anembodiment of this disclosure.

FIG. 4 is a process flow diagram of the apparatus used for the reactionof CO and H₂ in the experiment of Example 8.

FIG. 5 is a schematic of a high shear system comprising external highshear mixing/dispersing according to an embodiment of this disclosure.

FIG. 6 is a schematic of a method of producing synthesis gas accordingto an embodiment of this disclosure.

FIG. 7 is a schematic of a method of utilizing synthesis gas accordingto an embodiment of this disclosure.

FIG. 8 is a schematic of a method of catalytically reacting synthesisgas to produce FT products according to an embodiment of thisdisclosure.

NOTATION AND NOMENCLATURE

As used herein, the term “dispersion” refers to a liquefied mixture thatcontains at least two distinguishable substances (or “phases”) that willnot readily mix and dissolve together. As used herein, a “dispersion”comprises a “continuous” phase (or “matrix”), which holds thereindiscontinuous droplets, bubbles, and/or particles of the other phase orsubstance. The term dispersion may thus refer to foams comprising gasbubbles suspended in a liquid continuous phase, emulsions in whichdroplets of a first liquid are dispersed throughout a continuous phasecomprising a second liquid with which the first liquid is immiscible,and continuous liquid phases throughout which solid particles aredistributed. As used herein, the term “dispersion” encompassescontinuous liquid phases throughout which gas bubbles are distributed,continuous liquid phases throughout which solid particles (e.g., solidcatalyst) are distributed, continuous phases of a first liquidthroughout which droplets of a second liquid that is substantiallyinsoluble in the continuous phase are distributed, and liquid phasesthroughout which any one or a combination of solid particles, immiscibleliquid droplets, and gas bubbles are distributed. Hence, a dispersioncan exist as a homogeneous mixture in some cases (e.g., liquid/liquidphase), or as a heterogeneous mixture (e.g., gas/liquid, solid/liquid,or gas/solid/liquid), depending on the nature of the materials selectedfor combination. A dispersion may comprise, for example, bubbles of gas(e.g. synthesis gas) and/or particles of carbonaceous material in aliquid phase (e.g. slurry liquid and/or liquid Fischer-Tropschhydrocarbons)

The term “oxygenate is used herein to refer to substances that have beeninfused with oxygen. For example, the term refers to any oxygencomprising hydrocarbon such as high octane gasoline or diesel, suitableto drive combustion engines, as well as to oxygenated fuels sometimesemployed as gasoline additives to reduce carbon monoxide that is createdduring the burning of the fuel. The term “oxygenate” includes, but isnot limited to, aldehydes such as formaldehyde, methyl formate, andformic acid as well as oxygenates based on alcohols including: methanol,ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, 2-ethylhexanol, furfuryl alcohol, benzyl alcohol, isobutyl alcohol, andgasoline grade t-butanol (GTBA). Other oxygenates include carbonylcompounds such as ketones, esters, amides and anhydrides.

The terms “simple alkane” and “low molecular weight alkane” are usedherein to refer to low carbon number alkanes including methane, propane,and butane, which are gaseous at room temperature and atmosphericpressure.

The term “light gas” as utilized herein refers to a gas comprisingcarbon dioxide, simple alkanes having from one to five carbon atoms or acombination thereof.

Use of the phrase, ‘all or a portion of’ is used herein to mean ‘all ora percentage of the whole’ or ‘all or some components of.’

The term “catalytic surface” is used herein to refer to a surface in adevice that is constructed with catalytic material (such as metals,alloys, etc.) so that catalytic activity is manifested when suitablesubstance comes in touch with said catalytic surface. The use of theterm “catalytic surface” in this document includes all such surfacesregardless of the shape and size of surface, material of construct,method of make, degree of activity, or purpose of use.

The term “multifunctional catalyst” is used herein to refer to acatalyst that has more than one function of promoting two or morereactions when necessary reactants are present. For example, suchmultifunctional catalyst is a blend of two compatible catalysts whereinone catalyst promotes Fischer-Tropsch reactions and the other promotesalcohol forming reactions.

Certain terms are used throughout the following description and claimsto refer to particular system components. This document does not intendto distinguish between components that differ in name but not function.In the following discussion and in the claims, the terms “including” and“comprising” are used in an open-ended fashion, and thus should beinterpreted to mean “including, but not limited to . . . ”.

DETAILED DESCRIPTION

Conversion of Light Gas to Hydrocarbons/Organic Oxygenates

High shear systems and methods for improving conversion of light gas tohydrocarbons and/or organic oxygenates are disclosed. The system andmethod may be used to produce Syngas for further processing orhydrocarbons or hydrocarbon mixtures suitable for driving conventionalcombustion engines or hydrocarbons suitable for further industrialprocessing or other commercial use. Intermediate products such asmethanol or dimethyl ether may also be generated by the processdisclosed herein. In an embodiment, the overall process comprises theconversion of gas selected from carbon dioxide, methane, ethane,propane, butane, pentane and combinations thereof to hydrocarbons withcarbon numbers greater than 2, preferably C₅-C₁₀ hydrocarbons and/oroxygenates, such as methanol, acetic acid. In other instances, themethod comprises the use of high shear technology for the directconversion of methane (a major component of available natural gas) toliquid hydrocarbons, primarily organic oxygenates and other liquids. Theorganic oxygenate product may primarily comprise alcohols. Inembodiments, the organic oxygenate product comprises methanol. Inembodiments, methanol and carbon dioxide are converted into organicoxygenate product comprising ethanol. In embodiments the processinvolves production of Syngas from a carbonaceous material followed byconversion to a hydrocarbon liquid.

The present disclosure provides a system and process for the productionof hydrocarbons and/or oxygenates from light gas comprising carbondioxide and/or at least one C1-C5 alkane using at least one high shearreactor device to dissociate reactor feedstock into free radicals byproviding intimate contact of reactants and promoting chemical reactionsbetween multiphase reactants. The resulting hydrogen and/or oxygenradicals react with carbon dioxide and/or alkane to yield the productcomprising hydrocarbons and/or oxygenates. The high shear device makesfavorable reaction(s) that may not be favorable using conventionalreactors and operating conditions (i.e. when AG based on globalconditions is positive).

In one embodiment, the process comprises providing water and carbondioxide gas into a high shear reactor. Within the high shear reactorsystem the water and carbon dioxide may be dissociated into components.Subsequently, the components recombine to produce a product comprisinghigher carbon number (i.e. C₂₊, preferably C₅-C₁₀) hydrocarbons and/oroxygenates. The process comprises the use of at least one external highshear device to provide for production of oxygenates and/or hydrocarbonswithout the need for large volume reactors. In embodiments, the additionof water serves to assist in steam stripping of organics present invessel 10.

Another aspect of this disclosure is a process for production ofhydrocarbons and/or oxygenates from carbon dioxide and/or methane and asource of hydrogen such as simple hydrocarbons or other hydrocarbonsource. Water may also optionally or additionally be present as a sourceof free hydrogen and hydroxyl radicals. In embodiments of the method,the hydrogen source is selected from water, lower alkanes, andcombinations thereof. The reaction may be catalyzed with catalyticcompounds known to act as dehydrogenation catalyst. In embodiments, thehydrogen source may be a gas, e.g. hydrogen gas, or hydrogen dissociatedin HSD 40 from simple gaseous alkane and the liquid in line 21 may be acarrier, such as poly ethylene glycol.

In accordance with certain embodiments, a method is presented forproducing product comprising at least one selected from C₂₊hydrocarbons, oxygenates, and combinations thereof from light gascomprising one or more of carbon dioxide, methane, ethane, propane,butane, pentane, and methanol, the method comprising forming adispersion of light gas in the liquid feed, wherein the dispersion isformed at least in part with high shear forces, and wherein at least oneof the liquid feed and the light gas is a hydrogen source. Forming adispersion may comprise generating bubbles of light gas having a meandiameter in the range of about 0.1 to about 1.5 micron. In embodiments,the gas bubbles have a mean diameter less than about 0.4 micron.

In some embodiments, the high shear forces are produced with at leastone high shear device. The at least one high shear device may compriseat least one generator comprising a stator and a complementary rotor.The rotor and stator may be separated by a minimum clearance in therange of from about 0.02 mm to about 3 mm. In embodiments, forming thedispersion comprises a tip speed of the rotor of greater than 5.0 m/s(1000 ft/min). In embodiments, forming the dispersion comprises a tipspeed of the rotor of greater than 20 m/s (4000 ft/min). In embodiments,the at least one high shear device comprises at least two generators.Forming the dispersion may comprise subjecting a mixture of the lightgas and the liquid feed to a shear rate of greater than about 20,000s⁻¹. The high shear device may produce a local pressure of at leastabout 1034.2 MPa (150,000 psi) at the tip of the rotor during formationof the dispersion. The energy expenditure of the high shear device maybe greater than 1000 W/m³ during formation of the dispersion.

In some embodiments of the method for producing product comprising atleast one selected from C₂₊ hydrocarbons, oxygenates, and combinationsthereof from light gas, the dispersion further comprises a catalyst. Thecatalyst may comprise ruthenium. The catalyst may comprise rutheniumtrichloride heptahydrate. The method may further comprise introducingthe dispersion into a fixed bed reactor comprising a bed of catalyst.The fixed bed of catalyst may comprise ruthenium carbonyl.

Also disclosed herein is a method for producing product comprising atleast one selected from liquid oxygenates, C₂₊ hydrocarbons, andcombinations thereof comprising subjecting a fluid mixture comprising alight gas comprising carbon dioxide, methane, or both and a liquidmedium to a shear rate greater than 20,000 s⁻¹ to produce a dispersionof light gas in a continuous phase of the liquid, wherein the dispersionis formed at least in part with at least one high shear device, the atleast one high shear device configured to produce a dispersion ofbubbles of the light gas in the liquid medium, and introducing thedispersion into a reactor from which the product comprising at least oneselected from liquid oxygenates, C₂₊ hydrocarbons, and combinationsthereof is removed. The method may further comprise separating thereactor product into a gas stream and a liquid product stream comprisingliquid product, and recycling at least a portion of the gas stream tothe external high shear device. In embodiments, the dispersion has anaverage bubble diameter in the range of about 0.1 to about 1.5 micron.In embodiments, the dispersion has an average bubble diameter of lessthan 1 micron. The dispersion may be stable for at least about 15minutes at atmospheric pressure. In embodiments, the high shear devicecomprises at least two generators. The dispersion may further compriseat least one catalyst.

Also disclosed herein is a system for converting a gas comprising carbondioxide, methane, ethane, propane, butane, or a combination thereof toproduct comprising at least one selected from liquid oxygenates, C₂₊hydrocarbons, and combinations thereof, the system comprising at leastone high shear mixing device comprising at least one generatorcomprising a rotor and a stator separated by a shear gap, wherein theshear gap is the minimum distance between the rotor and the stator, andwherein the high shear mixing device is capable of producing a tip speedof the rotor of greater than 22.9 m/s (4,500 ft/min), and a pumpconfigured for delivering a mixture comprising light gas and a liquidmedium to the high shear mixing device. The system may further comprisea reactor disposed between the at least one high shear device and thepump, the reactor comprising a product outlet and an inlet configured toreceive the dispersion from the dispersion outlet of the at least onehigh shear device. The at least one high shear device may comprise atleast two generators. The shear rate provided by one generator may begreater than the shear rate provided by another generator. The at leastone high shear mixing device may be configured for producing adispersion of light gas bubbles in a liquid phase comprising liquidmedium; wherein the dispersion has a mean bubble diameter of less than400 nm. The at least one high shear mixing device may be capable ofproducing a tip speed of the rotor of at least 40.1 m/s (7,900 ft/min).The system may comprise at least two high shear mixing devices.

Some embodiments of the system potentially make possible the productionof organic liquid product from gas comprising carbon dioxide, methane,ethane, propane, butane, pentane, methanol or a combination thereofwithout the need for large volume reactors, via use of an externalpressurized high shear reactor.

Overview.

The rate of chemical reactions involving liquids, gases and solidsdepend on time of contact, temperature, and pressure. In cases where itis desirable to react two or more raw materials of different phases(e.g. solid and liquid; liquid and gas; solid, liquid and gas), one ofthe limiting factors controlling the rate of reaction involves thecontact time of the reactants. In the case of heterogeneously catalyzedreactions there is the additional rate limiting factor of having thereacted products removed from the surface of the catalyst to permit thecatalyst to catalyze further reactants. Contact time for the reactantsand/or catalyst is often controlled by mixing which provides contactwith two or more reactants involved in a chemical reaction.

A reactor assembly that comprises an external high shear device or mixeras described herein makes possible decreased mass transfer limitationsand thereby allows the reaction to more closely approach kineticlimitations. When reaction rates are accelerated, residence times may bedecreased, thereby increasing obtainable throughput. Product yield maybe increased as a result of the high shear system and process.Alternatively, if the product yield of an existing process isacceptable, decreasing the required residence time by incorporation ofsuitable high shear may allow for the use of lower temperatures and/orpressures than conventional processes.

The present invention utilizes innovative technology to produce organicproduct comprising hydrocarbons and/or liquid oxygenates from light gassuch as carbon dioxide and/or simple alkanes. The light gas isintimately mixed with a liquid medium. At least one of the light gas andthe liquid medium serves as hydrogen source. The hydrogen source may be,for example, water and/or hydrocarbons. A high shear reactor device andoptionally a catalyst may dissociate reactants into free radicalsallowing them to reform into product comprising hydrocarbons andoxygenates.

The system comprises the use of high shear technology for the conversionof carbon dioxide (a major greenhouse gas) and/or simple alkanes toproducts comprising liquid hydrocarbons, organic oxygenates orcombinations thereof. The herein disclosed process and system for theproduction of hydrocarbons and/or liquid oxygenates via multiphaseconversion of carbon dioxide and/or light gas, and a dehydrogenationcatalyst employs an external high shear mechanical device to providerapid contact and mixing of chemical ingredients in a controlledenvironment in a high shear device. The use of at least one high sheardevice reduces mass transfer limitations on the reaction(s) thusincreasing rates of mass transfer and enabling reactions to more closelyapproach kinetic limitations and also producing localized non-idealconditions that permit reactions to occur that would not otherwise beexpected to occur based on Gibbs free energy predictions, as discussedfurther hereinbelow.

System for Production of Liquids from Light Gas.

A high shear system for the production of hydrocarbons and/or liquidoxygenates from light gas will now be described in relation to FIG. 1,which is a process flow diagram of a representative high shear system100 for the production of organic oxygenates/hydrocarbons via conversionof light gas. The basic components of a representative system includeexternal high shear mixing device (HSD) 40, vessel 10, and pump 5. Asshown in FIG. 1, high shear device 40 is located external tovessel/reactor 10. Each of these components is further described in moredetail below. Line 21 is connected to pump 5 for introducing liquidmedium. Line 13 connects pump 5 to HSD 40, and line 18 connects HSD 40to vessel 10. One or more line may be connected to line 13 forintroducing reactant gas (e.g., carbon dioxide and/or methane gas). Forexample, in the embodiment in FIG. 1, lines 22 and 23 are connected toline 13. Alternatively, lines 22 and/or 23 may be connected to an inletof HSD 40. Line 17 may be connected to vessel 10 for removal ofunreacted reactant gas and/or reaction product gases. Product outletline 16 is connected to vessel 10 for removal of liquids from vessel 10.In embodiments, product line 16 may be connected to line 21 or line 13,to provide for multi-pass operation, if desired.

Additional components may be incorporated between vessel 10, externalhigh shear device 40, and pump 5 in some applications of the process, aswill become apparent upon reading the description of the high shearprocess for production of organic product described hereinbelow. Forexample, high shear system 100 may further comprise condenser 30,compressor 50, feed pump 4, high pressure pump 6, or a combinationthereof. As shown in FIG. 1, high shear system 100 may further compriseone or more additional pumps, such as feed pump 4, booster pump 6, orother pumps as necessary. Heat exchangers may be positioned throughoutsystem 100. In embodiments, temperature control equipment is internal tovessel 10, or positioned on a line within system 100. For example, inthe embodiment of FIG. 1, heat exchanger H1 is associated with vessel10, heat exchanger H2 is positioned on line 21, and heat exchanger H3 ispositioned on line 13. A heat exchanger may be positioned on line 16 ofvessel 10 and may serve to adjust the temperature of reaction productsexiting vessel 10.

High Shear Mixing Device.

External high shear mixing device (HSD) 40, also sometimes referred toas a high shear device or high shear mixing device, is configured forreceiving an inlet stream, via line 13, comprising liquid medium anddispersible light gas. Alternatively, HSD 40 may be configured forreceiving the liquid and gaseous reactant streams via separate inletlines (not shown). Although only one high shear device is shown in FIG.1, it should be understood that some embodiments of the system may havetwo or more high shear mixing devices arranged either in series orparallel flow. HSD 40 is a mechanical device that utilizes one or moregenerator comprising a rotor/stator combination, each of which has a gapbetween the stator and rotor. The gap between the rotor and the statorin each generator set may be fixed or may be adjustable. HSD 40 isconfigured in such a way that it is capable of producing submicron andmicron-sized bubbles in a reactant mixture flowing through the highshear device. The high shear device comprises an enclosure or housing sothat the pressure and temperature of the reaction mixture may becontrolled.

High shear mixing devices are generally divided into three generalclasses, based upon their ability to mix fluids. Mixing is the processof reducing the size of particles or inhomogeneous species within thefluid. One metric for the degree or thoroughness of mixing is the energydensity per unit volume that the mixing device generates to disrupt thefluid particles. The classes are distinguished based on delivered energydensities. Three classes of industrial mixers having sufficient energydensity to consistently produce mixtures or emulsions with particlesizes in the range of submicron to 50 microns include homogenizationvalve systems, colloid mills and high speed mixers. In the first classof high energy devices, referred to as homogenization valve systems,fluid to be processed is pumped under very high pressure through anarrow-gap valve into a lower pressure environment. The pressuregradients across the valve and the resulting turbulence and cavitationact to break-up any particles in the fluid. These valve systems are mostcommonly used in milk homogenization and can yield average particlesizes in the submicron to about 1 micron range.

At the opposite end of the energy density spectrum is the third class ofdevices referred to as low energy devices. These systems usually havepaddles or fluid rotors that turn at high speed in a reservoir of fluidto be processed, which in many of the more common applications is a foodproduct. These low energy systems are customarily used when averageparticle sizes of greater than 20 microns are acceptable in theprocessed fluid.

Between the low energy devices and homogenization valve systems, interms of the mixing energy density delivered to the fluid, are colloidmills and other high speed rotor-stator devices, which are classified asintermediate energy devices. A typical colloid mill configurationincludes a conical or disk rotor that is separated from a complementary,liquid-cooled stator by a closely-controlled rotor-stator gap, which iscommonly between 0.0254 mm to 10.16 mm (0.001-0.40 inch). Rotors areusually driven by an electric motor through a direct drive or beltmechanism. As the rotor rotates at high rates, it pumps fluid betweenthe outer surface of the rotor and the inner surface of the stator, andshear forces generated in the gap process the fluid. Many colloid millswith proper adjustment achieve average particle sizes of 0.1-25 micronsin the processed fluid. These capabilities render colloid millsappropriate for a variety of applications including colloid andoil/water-based emulsion processing such as that required for cosmetics,mayonnaise, or silicone/silver amalgam formation, to roofing-tar mixing.

Tip speed is the circumferential distance traveled by the tip of therotor per unit of time. Tip speed is thus a function of the rotordiameter and the rotational frequency. Tip speed (in meters per minute,for example) may be calculated by multiplying the circumferentialdistance transcribed by the rotor tip, 2πR, where R is the radius of therotor (meters, for example) times the frequency of revolution (forexample revolutions per minute, rpm). A colloid mill, for example, mayhave a tip speed in excess of 22.9 m/s (4500 ft/min) and may exceed 40m/s (7900 ft/min). For the purpose of this disclosure, the term ‘highshear’ refers to mechanical rotor stator devices (e.g., colloid mills orrotor-stator dispersers) that are capable of tip speeds in excess of 5.1m/s. (1000 ft/min) and require an external mechanically driven powerdevice to drive energy into the stream of products to be reacted. Forexample, in HSD 40, a tip speed in excess of 22.9 m/s (4500 ft/min) isachievable, and may exceed 40 m/s (7900 ft/min). In some embodiments,HSD 40 is capable of delivering at least 300 L/h at a tip speed of atleast 22.9 m/s (4500 ft/min). The power consumption may be about 1.5 kW.HSD 40 combines high tip speed with a very small shear gap to producesignificant shear on the material being processed. The amount of shearwill be dependent on the viscosity of the fluid. Accordingly, a localregion of elevated pressure and temperature is created at the tip of therotor during operation of the high shear device. In some cases thelocally elevated pressure is about 1034.2 MPa (150,000 psi). In somecases the locally elevated temperature is about 500° C. In some cases,these local pressure and temperature elevations may persist for nano orpico seconds.

An approximation of energy input into the fluid (kW/L/min) can beestimated by measuring the motor energy (kW) and fluid output (L/min).As mentioned above, tip speed is the velocity (ft/min or m/s) associatedwith the end of the one or more revolving elements that is creating themechanical force applied to the reactants. In embodiments, the energyexpenditure of HSD 40 is greater than 1000 W/m³. In embodiments, theenergy expenditure of HSD 40 is in the range of from about 3000 W/m³ toabout 7500 W/m³.

The shear rate is the tip speed divided by the shear gap width (minimalclearance between the rotor and stator). The shear rate generated in HSD40 may be in the greater than 20,000 s⁻¹. In some embodiments the shearrate is at least 40,000 s⁻¹. In some embodiments the shear rate is atleast 100,000 s⁻¹. In some embodiments the shear rate is at least500,000 s⁻¹. In some embodiments the shear rate is at least 1,000,000s⁻¹. In some embodiments the shear rate is at least 1,600,000 s⁻¹. Inembodiments, the shear rate generated by HSD 40 is in the range of from20,000 s⁻¹ to 100,000 s⁻¹. For example, in one application the rotor tipspeed is about 40 m/s (7900 ft/min) and the shear gap width is 0.0254 mm(0.001 inch), producing a shear rate of 1,600,000 s⁻¹. In anotherapplication the rotor tip speed is about 22.9 m/s (4500 ft/min) and theshear gap width is 0.0254 mm (0.001 inch), producing a shear rate ofabout 901,600 s⁻¹.

HSD 40 is capable of dispersing or transporting light gas into a mainliquid phase (continuous phase) with which it would normally beimmiscible, at conditions such that at least a portion of the gas isconverted to an organic product comprising C₂₊ hydrocarbons, oxygenates,or a combination thereof. The liquid medium may comprise at least onehydrogen source (e.g. simple liquid hydrocarbon or water). Inembodiments, the liquid medium further comprises a catalyst. In someembodiments, HSD 40 comprises a colloid mill. Suitable colloidal millsare manufactured by IKA® Works, Inc. Wilmington, N.C. and APV NorthAmerica, Inc. Wilmington, Mass., for example. In some instances, HSD 40comprises the DISPAX REACTOR® of IKA® Works, Inc.

The high shear device comprises at least one revolving element thatcreates the mechanical force applied to the reactants. The high sheardevice comprises at least one stator and at least one rotor separated bya clearance. For example, the rotors may be conical or disk shaped andmay be separated from a complementarily-shaped stator. In embodiments,both the rotor and stator comprise a plurality ofcircumferentially-spaced teeth. In some embodiments, the stator(s) areadjustable to obtain the desired shear gap between the rotor and thestator of each generator (rotor/stator set). Grooves between the teethof the rotor and/or stator may alternate direction in alternate stagesfor increased turbulence. Each generator may be driven by any suitabledrive system configured for providing the necessary rotation.

In some embodiments, the minimum clearance (shear gap width) between thestator and the rotor is in the range of from about 0.0254 mm (0.001inch) to about 3.175 mm (0.125 inch). In certain embodiments, theminimum clearance (shear gap width) between the stator and rotor isabout 1.52 mm (0.060 inch). In certain configurations, the minimumclearance (shear gap) between the rotor and stator is at least 1.78 mm(0.07 inch). The shear rate produced by the high shear device may varywith longitudinal position along the flow pathway. In some embodiments,the rotor is set to rotate at a speed commensurate with the diameter ofthe rotor and the desired tip speed. In some embodiments, the high sheardevice has a fixed clearance (shear gap width) between the stator androtor. Alternatively, the high shear device has adjustable clearance(shear gap width).

In some embodiments, HSD 40 comprises a single stage dispersing chamber(i.e., a single rotor/stator combination, a single generator). In someembodiments, high shear device 40 is a multiple stage inline disperserand comprises a plurality of generators. In certain embodiments, HSD 40comprises at least two generators. In other embodiments, high sheardevice 40 comprises at least 3 high shear generators. In someembodiments, high shear device 40 is a multistage mixer whereby theshear rate (which, as mentioned above, varies proportionately with tipspeed and inversely with rotor/stator gap width) varies withlongitudinal position along the flow pathway, as further describedherein below.

In some embodiments, each stage of the external high shear device hasinterchangeable mixing tools, offering flexibility. For example, the DR2000/4 DISPAX REACTOR® of IKA® Works, Inc. Wilmington, N.C. and APVNorth America, Inc. Wilmington, Mass., comprises a three stagedispersing module. This module may comprise up to three rotor/statorcombinations (generators), with choice of fine, medium, coarse, andsuper-fine for each stage. This allows for creation of dispersionshaving a narrow distribution of the desired bubble size (e.g., light gasbubbles). In some embodiments, each of the stages is operated withsuper-fine generator. In some embodiments, at least one of the generatorsets has a rotor/stator minimum clearance (shear gap width) of greaterthan about 5.0 mm (0.20 inch). In alternative embodiments, at least oneof the generator sets has a minimum rotor/stator clearance of greaterthan about 1.78 mm (0.07 inch).

Referring now to FIG. 2, there is presented a longitudinal cross-sectionof a suitable high shear device 200. High shear device 200 of FIG. 2 isa dispersing device comprising three stages or rotor-statorcombinations. High shear device 200 is a dispersing device comprisingthree stages or rotor-stator combinations, 220, 230, and 240. Therotor-stator combinations may be known as generators 220, 230, 240 orstages without limitation. Three rotor/stator sets or generators 220,230, and 240 are aligned in series along drive shaft 250.

First generator 220 comprises rotor 222 and stator 227. Second generator230 comprises rotor 223, and stator 228. Third generator 240 comprisesrotor 224 and stator 229. For each generator the rotor is rotatablydriven by input 250 and rotates about axis 260 as indicated by arrow265. The direction of rotation may be opposite that shown by arrow 265(e.g., clockwise or counterclockwise about axis of rotation 260).Stators 227, 228, and 229 are fixably coupled to the wall 255 of highshear device 200.

As mentioned hereinabove, each generator has a shear gap width which isthe minimum distance between the rotor and the stator. In the embodimentof FIG. 2, first generator 220 comprises a first shear gap 225; secondgenerator 230 comprises a second shear gap 235; and third generator 240comprises a third shear gap 245. In embodiments, shear gaps 225, 235,245 have widths in the range of from about 0.025 mm to about 10.0 mm.Alternatively, the process comprises utilization of a high shear device200 wherein the gaps 225, 235, 245 have a width in the range of fromabout 0.5 mm to about 2.5 mm. In certain instances the shear gap widthis maintained at about 1.5 mm. Alternatively, the width of shear gaps225, 235, 245 are different for generators 220, 230, 240. In certaininstances, the width of shear gap 225 of first generator 220 is greaterthan the width of shear gap 235 of second generator 230, which is inturn greater than the width of shear gap 245 of third generator 240. Asmentioned above, the generators of each stage may be interchangeable,offering flexibility. High shear device 200 may be configured so thatthe shear rate will increase stepwise longitudinally along the directionof the flow 260.

Generators 220, 230, and 240 may comprise a coarse, medium, fine, andsuper-fine characterization. Rotors 222, 223, and 224 and stators 227,228, and 229 may be toothed designs. Each generator may comprise two ormore sets of rotor-stator teeth. In embodiments, rotors 222, 223, and224 comprise more than 10 rotor teeth circumferentially spaced about thecircumference of each rotor. In embodiments, stators 227, 228, and 229comprise more than ten stator teeth circumferentially spaced about thecircumference of each stator. In embodiments, the inner diameter of therotor is about 12 cm. In embodiments, the diameter of the rotor is about6 cm. In embodiments, the outer diameter of the stator is about 15 cm.In embodiments, the diameter of the stator is about 6.4 cm. In someembodiments the rotors are 60 mm and the stators are 64 mm in diameter,providing a clearance of about 4 mm. In certain embodiments, each ofthree stages is operated with a super-fine generator, comprising a sheargap of between about 0.025 mm and about 4 mm. For applications in whichsolid particles are to be sent through high shear device 40, theappropriate shear gap width (minimum clearance between rotor and stator)may be selected for an appropriate reduction in particle size andincrease in particle surface area. In embodiments, this may bebeneficial for increasing surface area of solid catalyst by shearing anddispersing the particles.

High shear device 200 is configured for receiving from line 13 areaction mixture at inlet 205. The reaction mixture comprises gas as thedispersible phase and liquid medium as the continuous phase. The feedstream may further comprise a particulate solid catalyst component. Feedstream entering inlet 205 is pumped serially through generators 220,230, and then 240, such that a dispersion is formed. The dispersionexits high shear device 200 via outlet 210 (and line 18 of FIG. 1). Therotors 222, 223, 224 of each generator rotate at high speed relative tothe fixed stators 227, 228, 229, providing a high shear rate. Therotation of the rotors pumps fluid, such as the feed stream enteringinlet 205, outwardly through the shear gaps (and, if present, throughthe spaces between the rotor teeth and the spaces between the statorteeth), creating a localized high shear condition. High shear forcesexerted on fluid in shear gaps 225, 235, and 245 (and, when present, inthe gaps between the rotor teeth and the stator teeth) through whichfluid flows process the fluid and create the dispersion. The productdispersion exits high shear device 200 via high shear outlet 210 (andline 18 of FIG. 1).

The produced dispersion has an average gas bubble size less than about 5μm. In embodiments, HSD 40 produces a dispersion having a mean bubblesize of less than about 1.5 μm. In embodiments, HSD 40 produces adispersion having a mean bubble size of less than 1 μm; preferably thebubbles are sub-micron in diameter. In certain instances, the averagebubble size is from about 0.1 μm to about 1.0 μm. In embodiments, HSD 40produces a dispersion having a mean bubble size of less than 400 nm. Inembodiments, HSD 40 produces a dispersion having a mean bubble size ofless than 100 nm. High shear device 200 produces a dispersion comprisingdispersed gas bubbles capable of remaining dispersed at atmosphericpressure for at least about 15 minutes.

Not to be limited by theory, it is known in emulsion chemistry thatsub-micron particles, or bubbles, dispersed in a liquid undergo movementprimarily through Brownian motion effects. The bubbles in the productdispersion created by high shear device 200 may have greater mobilitythrough boundary layers of solid catalyst particles (if present),thereby further facilitating and accelerating the conversion reactionthrough enhanced transport of reactants in a heterogeneous reactionmixture.

In certain instances, high shear device 200 comprises a DISPAX REACTOR®of IKA® Works, Inc. Wilmington, N.C. and APV North America, Inc.Wilmington, Mass. Several models are available having variousinlet/outlet connections, horsepower, tip speeds, output rpm, and flowrate. Selection of the high shear device will depend on throughputrequirements and desired particle or bubble size in dispersion in line18 (FIG. 1) exiting outlet 210 of high shear device 200. IKA® model DR2000/4, for example, comprises a belt drive, 4M generator, PTFE sealingring, inlet flange 25.4 mm (1 inch) sanitary clamp, outlet flange 19 mm(¾ inch) sanitary clamp, 2HP power, output speed of 7900 rpm, flowcapacity (water) approximately 300-700 L/h (depending on generator), atip speed of from 9.4-41 m/s (1850 ft/min to 8070 ft/min).

Vessel.

Once dispersed, the dispersion exits high shear device 40 via high sheardevice outlet dispersion line 18 and is introduced into vessel 10.Vessel 10 may comprise any type of reactor in which multiphase reactioncan be propagated to carry out the conversion reaction(s). For instance,a continuous or semi-continuous stirred tank reactor, or one or morebatch reactors may be employed in series or in parallel. In someembodiments, vessel 10 is a tower reactor. In some applications, vessel10 is a tubular reactor, and in others a tubular reactor ormulti-tubular reactor.

Any number of reactor inlet lines is envisioned, with one shown in FIG.1 (line 3). An inlet line may be connected to vessel 10 for receiving acatalyst solution or slurry during operation of the system withheterogeneous catalyst. In embodiments, water is injected into vessel 10to assist in steam stripping of organics present within vessel 10. Inthis manner, a portion of the organic product may be stripped with steamand exit vessel 10 in line 17 rather than in line 16. Vessel 10 maycomprise an exit line 17 for vent gas, and an outlet product line 16 fora product stream. In embodiments, vessel 10 comprises a plurality ofreactor product lines 16.

Conversion of carbon dioxide and/or simple hydrocarbons to organicoxygenates/hydrocarbons will occur wherever suitable time, temperatureand pressure conditions exist. In this sense hydrogenation could occurat any point in the flow diagram of FIG. 1 if temperature and pressureconditions are suitable. The reaction carried out by high shear system100 may comprise a homogeneous catalytic reaction in which the catalystis in the same phase as another component of the reaction mixture or aheterogeneous catalytic reaction involving a solid catalyst. Where acirculated catalyst is utilized, reaction is more likely to occur atpoints outside vessel 10 shown of FIG. 1. Nonetheless a discretereactor/vessel 10 is often desirable to allow for increased residencetime, agitation and heating and/or cooling, as well as for separationand recovery of volatile reaction products and recycling of non-reactedgases. Thus, in some embodiments, high shear system 100 furthercomprises a vessel 10 downstream of the at least one high shear device,wherein an inlet of the vessel is fluidly connected with the dispersionoutlet of the high shear device. When a fixed bed reactor 10 isutilized, the reactor/vessel 10 may become the primary location for thereaction to occur.

Vessel 10 outlet line 16 may be fluidly connected to line 21, forexample via line 20, for recycle of a portion of the contents in line 16comprising liquid product to HSD 40. Alternatively, a separate outletline may connect vessel 10 with line 21 in some embodiments. In FIG. 1,high shear system 100 is configured for recycle of a portion of line 16.This configuration is one which lends itself to multi-pass operation,for example.

Vessel 10 may include one or more of the following components: stirringsystem, temperature control capabilities, pressure measurementinstrumentation, temperature measurement instrumentation, one or moreinjection points, and level regulator (not shown), as are known in theart of reaction vessel design. As shown in the embodiment of FIG. 1,vessel 10 may further comprise stirring system 31; heating and/orcooling capabilities H1, pressure measurement instrumentation,temperature measurement instrumentation, or a combination thereof. Forexample, stirring system 31 may include a motor driven mixer. Atemperature control apparatus H1 may comprise, for example, a heatingmantle or cooling coils. Alternatively, as much of the conversionreaction may occur within HSD 40 in some embodiments, vessel 10 mayserve primarily as a storage vessel in some cases. Although generallyless desired, in some applications vessel 10 may be omitted,particularly if multiple high shear devices/reactors are employed inseries, as further described below.

Heat Transfer Devices.

In addition to the above-mentioned heating/cooling capabilities ofvessel 10, other external or internal heat transfer devices for heatingor cooling a process stream are also contemplated in variations of theembodiments illustrated in FIG. 1. For example, temperature control maybe provided to vessel 10 via internal heat transfer devices as known toone skilled in the art. The use of external heating and/or cooling heattransfer devices is also contemplated. Some suitable locations for oneor more such heat transfer devices are between pump 5 and HSD 40,between HSD 40 and vessel 10, and between vessel 10 and pump 5 whensystem 100 is operated in multi-pass mode. Some non-limiting examples ofsuch heat transfer devices are shell, tube, plate, and coil heatexchangers, as are known in the art.

In the embodiment of high shear system 100 in FIG. 1, three heattransfer devices are used to control temperature throughout the system.Heat transfer device H1 is used to control the temperature of theproduct in vessel 10. Heat transfer device H2 is positioned on line 21for controlling temperature in line 21. Heat transfer device H3 servesto control the temperature of line 13 and thereby control thetemperature of the inlet feedstream to HSD 40. Use and configuration ofheating/cooling devices is for the purpose of carrying out the desiredreaction and may be altered accordingly as known to those of skill inthe art.

Pump(s)/Cold Trap.

Pump 5 is configured for either continuous or semi-continuous operation,and may be any suitable pumping device that is capable of providinggreater than 202.65 kPa (2 atm) pressure, alternatively greater than303.975 kPa (3 atm) pressure, to allow controlled flow through HSD 40and system 100. For example, a Roper Type 1 gear pump, Roper PumpCompany (Commerce Ga.) Dayton Pressure Booster Pump Model 2P372E, DaytonElectric Co (Niles, Ill.) is one suitable pump. All contact parts of thepump may comprise stainless steel, for example, 316 stainless steel. Insome embodiments of the system, pump 5 is capable of pressures greaterthan about 2026.5 kPa (20 atm). In embodiments, pump 5 produces a flowrate of liquid medium 21 of between about 0.5 and about 1 gallon/min. Inembodiments, pump 5 produces a flow rate of liquid medium 21 of about 1gallon/min.

In addition to pump 5, one or more additional, high pressure pump (notshown) may be included in the system illustrated in FIG. 1. For example,a booster pump, which may be similar to pump 5, may be included betweenHSD 40 and vessel 10 for boosting the pressure into vessel 10. In theembodiment of FIG. 1, high shear system 100 further comprises a highpressure pump 6 for boosting the pressure into vessel 10. When pump 6 isincorporated as a booster pump, pump 5 may be used as a throttlingpump/valve to reduce pressure to the high shear unit, thus reducing wearthereof. As still another example, a compressor type pump may bepositioned between line 17 and HSD 40 for recycling gas from vessel 10to an inlet of the high shear device.

As another example, a supplemental feed pump, which may be similar topump 5, may be included for introducing additional reactants or catalystinto vessel 10. In the embodiment of FIG. 1, for example, supplementalfeed pump 4 is used to introduce additional raw materials into vessel 10through injection line 3. Catalyst and make-up fluids may beperiodically or continuously added as needed to high shear system 100via feed pump 4 and injection point 3.

As shown in FIG. 1, high shear system 100 may further comprise a coldtrap, for example, within condenser 30, positioned on recycle line 17.The cold trap serves to take the recycle gases 17 into an ice coolerreceiver from which the gas in line 25 is piped to compressor 50 to beinjected into high shear device 40 via line 15. Condenser 30 comprisesan outlet line 24 for condensed product (e.g. any oxygenates and/orhydrocarbons) and an outlet line 25 for a recycle gas stream. Inembodiments, cold trap of condenser 30 serves to remove primarilyalcohols from recycle line 17 upstream of recirculation pump orcompressor 50. Recycle line 15 may be fluidly connected to line 13 forreintroduction of light gas to HSD 40, as shown in FIG. 1.

Production of Organic Product by Conversion of Light Gas.

Operation of high shear system 100 will now be discussed with referenceto FIG. 1. As shown in the embodiment of high shear system 100 in FIG.1, in embodiments, system 100 comprises two or more dispersible gasstreams. For example, in some embodiments, high shear system 100comprises dispersible gas line 22 and dispersible gas line 23. Inoperation for the conversion of light gas to organic product, adispersible light gas stream is introduced into system 100 via line 22and/or line 23, and combined in line 13 with a liquid stream.Dispersible gas in line 22 and/or line 23, compressed recycle fluid inline 15 and liquid medium in line 21 are introduced separately or as amixed stream into external high shear device 40. As shown in FIG. 1, inembodiments, dispersible gas stream in line 22 and/or line 23 isintroduced into liquid medium (which may comprise hydrogen source orhydrogen source and catalyst) and the combined gas/liquid (orgas/liquid/solid) stream is introduced into HSD 40.

Dispersible gas introduced into HSD 40 comprises light gas. The lightgas to be dispersed in HSD 40 may comprise methane, carbon dioxide, or acombination thereof. As sources of natural gas often comprise additionalgaseous components, the light gas introduced into line 13 via line 22,and/or line 23 may further comprise up to about 10% of additionalgaseous components. The additional gaseous components may be, forexample, ethane, propane, butane, pentane, methanol or a combinationthereof. In some embodiments, light gas comprises ethane, propane,butane, or a combination thereof, and light gas in line 23 comprisescarbon dioxide. In specific embodiments, light gas comprises methane. Inembodiments, dispersible light gas comprises carbon dioxide. Inembodiments, light gas comprises carbon dioxide and methane. Inembodiments, light gas comprises a 2:1 ratio of methane to carbondioxide. In embodiments, the light gas comprises carbon dioxide,hydrogen, and carbon monoxide. In embodiments, light gas is continuouslyfed into line 13. In embodiments, the feed rate of dispersible light gasis greater than about 50 cc/min. Alternatively, the feed rate ofdispersible light gas is greater than about 80 cc/min. Alternatively,the feed rate of dispersible light gas is greater than about 2300cc/min.

The liquid medium may be a variety of types. The liquid medium in line21 may comprise at least one hydrogen source. The at least one hydrogensource may be selected from water, hydrocarbons, and combinationsthereof. In embodiments, liquid medium is selected from water, lowermolecular weight liquid alkanes, paraffinic oils and combinationsthereof. The paraffinic oil may be either hydroprocessed petroleumderived oil, such as the Paralux oils as supplied by Chevron ProductsCompany or synthetic paraffin oils. Suitable synthetic paraffinic oilsinclude, for example, poly-alpha olefins (API) Group IV base oil as wellas hydrocracked/hydroisomerized (API) Group III base oils. Such Group(IV) base oil includes oil such as a low weight component ofPoly-ethylene-propylene. Petrochemical companies have developedprocesses involving catalytic conversion of feed stocks under pressurein the presence of hydrogen into high quality Group III minerallubricating oil. Additionally, GTL (Gas-To-Liquid) synthetic Group IIIbase stocks are available. Liquid medium may further comprise lithiumbromide. Liquid medium is desirably selected such that the componentsthereof do not flash to a considerable degree under conditions withinhigh shear device 40, but remain liquid therein. In some embodiments,liquid medium comprises polyethylene glycol (PEG).

In embodiments, the liquid medium and catalyst are mixed prior tointroduction into vessel 10. For example, paraffinic oil and catalyst(if used) may be initially charged into vessel 10 prior to sealingunits. In embodiments, catalyst is added to liquid medium in a stirredbeaker. In other embodiments, the liquid medium and catalyst areintroduced separately and mixed within vessel 10 via reactor agitator31. Additional reactants may be added to vessel 10 if desired for aparticular application, for example via feed pump 4 and vessel 10 inletline 3. Any number of vessel 10 inlet lines is envisioned. High shearsystem 100 may then be sealed and vessel 10 evacuated. In embodiments,vessel 10 is purged with oxygen. For example, a vacuum may be pulled viareactor gas line 17.

Following evacuation, dispersible light gas may be injected into highshear system 100 until the pressure in vessel 10 reaches a desiredrange. In embodiments, dispersible light gas is introduced into highshear device 40 until a pressure of 206.8 kPa (30 psi) is attained invessel 10. Next, high shear device 40 may be placed in operation,reactor agitation via, for example, stirring system 31 continued, andhigh shear pumping of reactor fluids throughout high shear system 100commenced. At this point, the system may be a closed loop with noventing.

In embodiments, the dispersible light gas is fed directly into HSD 40,instead of being combined with the liquid medium in line 13. Pump 5 maybe operated to pump the liquid medium through line 21, and to buildpressure and feed HSD 40, providing a controlled flow throughout highshear device (HSD) 40 and high shear system 100. In some embodiments,pump 5 increases the pressure of the HSD inlet stream to greater than202.65 kPa (2 atm), alternatively greater than about 303.975 kPa (3atmospheres). In this way, high shear system 100 may combine high shearwith pressure to enhance reactant intimate mixing.

After pumping, the light gas and liquid medium are mixed within HSD 40,which serves to create a fine dispersion of the light gas in the liquidmedium. In HSD 40, the light gas and liquid medium are highly dispersedsuch that nanobubbles, submicron-sized bubbles, and/or microbubbles ofthe light gas are formed for superior dissolution into solution andenhancement of reactant mixing. For example, disperser IKA® model DR2000/4, a high shear, three stage dispersing device configured withthree rotors in combination with stators, aligned in series, may be usedto create the dispersion of dispersible light gas in liquid medium. Therotor/stator sets may be configured as illustrated in FIG. 2, forexample. The combined reactants enter the high shear device via line 13and enter a first stage rotor/stator combination. The rotors and statorsof the first stage may have circumferentially spaced first stage rotorteeth and stator teeth, respectively. The coarse dispersion exiting thefirst stage enters the second rotor/stator stage. The rotor and statorof the second stage may also comprise circumferentially spaced rotorteeth and stator teeth, respectively. The reduced bubble-size dispersionemerging from the second stage enters the third stage rotor/statorcombination, which may comprise a rotor and a stator having rotor teethand stator teeth, respectively. The dispersion exits the high sheardevice via line 18. In some embodiments, the shear rate increasesstepwise longitudinally along the direction of the flow, 260.

For example, in some embodiments, the shear rate in the firstrotor/stator stage is greater than the shear rate in subsequentstage(s). In other embodiments, the shear rate is substantially constantalong the direction of the flow, with the shear rate in each stage beingsubstantially the same.

The rotor(s) of HSD 40 may be set to rotate at a speed commensurate withthe diameter of the rotor and the desired tip speed. As described above,the high shear device (e.g., colloid mill or toothed rim disperser) haseither a fixed clearance between the stator and rotor or has adjustableclearance. In some embodiments of the process, the transport resistanceof the reactants is reduced by operation of the high shear device suchthat the velocity of the reaction is increased by greater than about 5%.In some embodiments of the process, the transport resistance of thereactants is reduced by operation of the high shear device such that thevelocity of the reaction is increased by greater than a factor of about5. In some embodiments, the velocity of the reaction is increased by atleast a factor of 10. In some embodiments, the velocity is increased bya factor in the range of about 10 to about 100 fold.

In some embodiments, HSD 40 delivers at least 300 L/h at a tip speed ofat least 4500 ft/min, and which may exceed 7900 ft/min (40 m/s). Thepower consumption may be about 1.5 kW. Although measurement ofinstantaneous temperature and pressure at the tip of a rotating shearunit or revolving element in HSD 40 is difficult, it is estimated thatthe localized temperature seen by the intimately mixed reactants is inexcess of 500° C. and at pressures in excess of 500 kg/cm² undercavitation conditions. The high shear mixing results in dispersion ofthe light gas in micron or submicron-sized bubbles. In some embodiments,the resultant dispersion has an average bubble size less than about 1.5μm. Accordingly, the dispersion exiting HSD 40 via line 18 comprisesmicron and/or submicron-sized gas bubbles. In some embodiments, the meanbubble size is in the range of about 0.4 μm to about 1.5 μm. In someembodiments, the resultant dispersion has an average bubble size lessthan 1 μm. In some embodiments, the mean bubble size is less than about400 nm, and may be about 100 nm in some cases. In many embodiments, thedispersion is able to remain dispersed at atmospheric pressure for atleast 15 minutes. In some embodiments, the average bubble size refers tothe average bubble diameter under reaction conditions.

Once dispersed, the resulting gas/liquid or gas/liquid/solid dispersionexits HSD 40 via line 18 and feeds into vessel 10, as illustrated inFIG. 1. Dispersion in line 18 may optionally undergo further processing(heating/cooling) as may be desired in a particular application prior toentering vessel 10. As a result of the intimate mixing of the reactantsprior to entering vessel 10, a significant portion of the chemicalreaction may take place in HSD 40. Accordingly, in some embodiments,reactor/vessel 10 may be used primarily for heating and separation ofproduct liquids from unreacted light gas and any product gas.Alternatively, or additionally, vessel 10 may serve as a primaryreaction vessel where most of the organic product is produced. Forexample, in embodiments, vessel 10 is a fixed bed reactor comprising afixed bed of catalyst.

Catalyst.

If a catalyst is used to promote the conversion reactions, the catalystmay be introduced as a slurry or catalyst stream into vessel 10, forexample via line 3. Alternatively, or additionally, catalyst may beadded elsewhere in system 100. For example, catalyst slurry may beinjected into line 21. In some embodiments, system 100 comprises aclosed slurry loop, and line 21 may contain liquid medium, liquidproduct, and/or catalyst recycled from line 16. In embodiments thecatalyst may be a fixed bed catalyst.

The system and method of this disclosure pair high shear and possiblycavitation to create conditions not only conducive to generating freehydrogen radicals but also having the potential to generate freehydroxyl radicals and perhaps even deoxygenate carbon dioxide directly.

In some embodiments of the disclosed method, light gas and water arecontacted with a catalyst for dissociating water and/or a catalyst fordissociating carbon dioxide and/or alkane. Such catalysts are commonlyused in water gas shift reactions.

The water gas shift (WGS) reaction is a well known catalytic reactionwhich is used, among other things, to generate hydrogen by chemicalreaction of CO with water vapor (H₂O) according to the followingstoichiometry:CO+H₂O→CO₂+H₂,  (1)wherein the reaction typically utilizes a catalyst. Typical catalystsemployed in this reaction are based on combinations of iron oxide withchromium at high temperatures (about 350° C.) or mixtures of copper andzinc materials at lower temperatures (about 200° C.).

Dehydrogenation catalysts also include numerous catalytic compositescomprising a platinum group component and a modifier metal componentselected from the group consisting of a tin component, germaniumcomponent, rhenium component, and mixtures thereof are known. Forexample related U.S. Pat. Nos. 3,632,503, 3,755,481, and 3,878,131disclose catalysts comprising a platinum group component, a tincomponent, and a germanium component on a porous carrier material.Compounds comprising rhenium are also well known for theirdehydrogenation properties.

Depending on reaction conditions and catalyst selectivity, simplealcohols such as methanol can be produced directly from light gas andwater by the method and system of this disclosure. Oxygen released underthe high shear conditions is available to react with other radicalscreated to produce simple alcohols. From methanol, dimethyl ether may beproduced. Dimethyl ether can then be utilized as a fuel either directlyor mixed with conventional fuels.

The overall chemistry and the energy balance of the process for lightgas comprising carbon dioxide is shown in Formulas 2 through 10. Theheat of reactions for formulae 2 through 9 is calculated from thecorresponding heats of formation. For a (—CH₂—) unit, the heat offormation is calculated as ⅛th of the heat of formation of octane.6H₂O(l)→6H₂(g)+3O₂(g) 1.710 kJ Electrical energy  (2)H₂O(l)→H⁺+OH⁻  (3)2CO₂(g)+2H₂(g)→2CO(g)+2H₂O(g) 86.2 kJ Heat  (4)2CO(g)+4H₂(g)→2CH₃OH(g) −181.6 kJ Heat  (5)2CH₃OH(g)→CH₃OCH₃(g)+H₂O(g) −24 kJ Heat  (6)CH₃OCH₃(g)→2(—CH₂—)(g)+H₂O(g) −110 kJ Heat  (7)2CO₂(g)+2H₂(g)→2O₂(g)+2(—CH₂—)(l) −229 kJ Heat balance  (8)4H₂O(g)→4H₂O(l) −176 kJ Heat of condensation  (9)2H₂O(l)+2CO₂(g)→3O₂(g)+2(—CH₂—)(l) 1305 kJ Energy balance  (10)

Without wishing to be limited by theory, formula 8 shows the balancedequation of all the reactions which are believed to occur after thedeoxygenating of CO₂ step, i.e., steps 4-7, and the total amount ofhydrocarbon generated. Formula 9 shows the heat of condensation for theproduced water that may be recycled in the process. The overall chemicalbalance for steps 2-6 and the calculated overall energy consumption ofthe process is shown in Formula 10.

Vessel/reactor 10 may be operated in either continuous orsemi-continuous flow mode, or it may be operated in batch mode. Thecontents of vessel 10 may be maintained at a specified reactiontemperature using heating and/or cooling capabilities (e.g., heater H1)and temperature measurement instrumentation. Pressure in the vessel maybe monitored using suitable pressure measurement instrumentation, andthe level of reactants in the vessel may be controlled using a levelregulator (not shown), employing techniques that are known to those ofskill in the art. The contents may be stirred continuously orsemi-continuously with, for example stirring system 31.

In embodiments, at least a portion of the reaction mixture in line 16comprising liquid medium, liquid product, and optional catalyst isrecirculated to HSD 40 for multi-pass operation. Line 16 may be fluidlyconnected to line 21 by line 20, for recycle of at least a portion ofline 16 to HSD 40. As shown in FIG. 1, heat transfer device H2 may serveto control the temperature of line 21.

Unreacted light gas along with any other gas in vessel 10 may exitvessel 10 via gas line 17. As shown in FIG. 1, in embodiments, gasrecovered from the vessel 10 headspace may be passed through a condenser30. Extraction of reactor gas from vessel 10 may be aided by, forexample, compressor 50. Condenser 30 may comprise a cooling coil andcold trap. Non condensed gases from condenser 30 may be introduced vialine 25 to a compressor 50. Compressed gas may be recycled via, forexample, line 15. Line 15 may introduce compressed material fromcompressor 50 injected into HSD 40, independently, or into line 13, line22, and/or line 23. Condensed liquid product 24 exiting condenser 30 isextracted from the system. Condensed liquid in line 24 comprisesreaction products that may be utilized by any means known in the art,for example sale thereof or conversion into various other chemicalproducts.

Temperature.

In some embodiments, use of the disclosed process comprising reactantmixing via external high shear device 40 permits conversion of light gasto organic product comprising oxygenates, hydrocarbons, or a combinationthereof. The temperature within high shear device 40 is desirably belowthe flash point of the liquid medium. In embodiments, the reactiontemperature is less than 220° C. In some embodiments, operatingconditions comprise a temperature in the range of from about 100° C. toabout 230° C. In some embodiments, the temperature is in the range ofabout 30° C. to about 40° C. In some embodiments, the temperature is inthe range of from about 160° C. to 180° C. In some specific embodiments,the reaction temperature is in the range of from about 155° C. to about160° C. In embodiments, the product profile changes with temperature invessel 10, and the reactor temperature may be adjusted to attain thedesired product profile. At increased temperatures, a greater quantityof lower molecular weight materials may be produced, while, at lowertemperatures, a greater quantity of higher molecular weight materialsmay be produced.

Pressure.

In some embodiments, the reaction pressure in vessel 10 is in the rangeof from about 202.65 kPa (2 atm) to about 5.6 MPa-6.1 MPa (55-60 atm).In some embodiments, reaction pressure is in the range of from about810.6 kPa to about 1.5 MPa (8 atm to about 15 atm). In embodiments,vessel 10 is operated at or near atmospheric pressure. In embodiments,reaction pressure is less than about 6895 kPa (1000 psi). Alternatively,in some embodiments, the operating pressure is less than about 3445 kPa(500 psi). In some embodiments, the operating pressure is less thanabout 3100 kPa (450 psi). In some embodiments, the operating pressure isless than about 1030 kPa (150 psi).

In some instances, it is desirable to further enhance the degree oflight gas conversion. Increasing reaction pressure increases reactionrate, but also increases wear of the materials constituting thereactors, the piping, and the mechanical parts of the plant, as well asthe ancillary devices. The superior dissolution and/or dispersionprovided by the external high shear mixing may allow a decrease inoperating pressure while maintaining or even increasing productproduction.

Multiple Pass Operation.

As shown in FIG. 1, it may be desirable to pass the contents of vessel10, or a fraction thereof, through HSD 40 during a second pass. In thiscase, line 16 may be connected to line 21 as indicated, such that atleast a portion of the contents of line 16 is recycled from vessel 10and pumped by pump 5 into line 13 and thence into HSD 40. Additionallight gas may be injected into line 13, or may be added directly intothe high shear device (not shown). In other embodiments, product in line16 may be further treated (for example, liquid product removedtherefrom) prior to recycle of a portion of the liquid in line 16 tohigh shear device 40. In some embodiments it may be desirable to passthe liquid medium and dispersible gas comprising carbon dioxide and/oralkane through high shear device 40 and then add optional catalyst intoline 13 during a second pass through HSD 40.

Multiple High Shear Mixing Devices.

In some embodiments, two or more high shear devices like HSD 40, orconfigured differently, are aligned in series, and are used to furtherenhance the reaction. Their operation may be in either batch orcontinuous mode. In some instances in which a single pass or “oncethrough” process is desired, the use of multiple high shear devices inseries may be advantageous. For example, in embodiments, outletdispersion in line 18 may be fed into a second high shear device. Whenmultiple high shear devices 40 are operated in series, additional lightgas may be injected into the inlet feedstream of each device. Althoughgenerally less desirable, in embodiments where multiple high sheardevices 40 are operated in series, vessel 10 may be omitted. In someembodiments, multiple high shear devices 40 are operated in parallel,and the outlet dispersions therefrom are introduced into one or morevessel 10.

Product/Downstream Processing.

Gas is removed from vessel 10 via gas outlet line 17. The gas in line 17may comprise unreacted light gas, H₂, as well as oxygenate and/orhydrocarbon product. Gas removed via reactor gas outlet 17 may befurther treated and its components recycled. For example, cold trap 30may be used to condense and remove from gas line 17 any productoxygenate and/or hydrocarbon that escapes vessel 10 in recycle gas line17. Condensate stream exiting condenser 30 via line 24 may compriseprimarily alcohols. In embodiments, the liquid product condensate streamin line 24 comprises methanol. In embodiments, liquid product condensatestream in line 24 comprises greater than 50% methanol. In embodiments,liquid product condensate stream in line 24 comprises greater than 65%methanol. In embodiments, liquid product condensate stream in line 24comprises about 68% methanol. In embodiments, methanol and carbondioxide are converted into organic oxygenate product comprising ethanol.

In some applications, the unconverted light gas removed from cold trap30 via line 25 is recovered and injected (directly or indirectly) backinto high shear device 40.

A portion of product in line 16 may be removed from vessel 10. Organicproduct in line 16 comprises liquid oxygenates, hydrocarbons, or acombination thereof in addition to liquid medium. The product stream maycomprise primarily hydrocarbons produced during reaction along withliquid medium. For example, in embodiments, product in line 16 compriseshydrocarbons in polyethylene glycol. In applications where ethane,butane, propane, and pentane are present in the light gas, the resultingproduct in line 16 may comprise product having a higher carbon numberthan when methane and carbon dioxide are utilized. In such instances,the product removed via line 16 may comprise greater amounts of mixedoxygenates and aldehydes.

The liquid product comprising oxygenate and/or hydrocarbon recoveredfrom product line 16 and/or condensate line 24 may then be used as afuel or utilized as a feed stock to another chemical processes, as knownto those of skill in the art. For instance, methanol produced by theprocess may serve as a feed to a process for making formaldehyde.

Enhanced Oil Recovery with Liquids Produced from Methane.

Low API (viscous) oil is often difficult to recover due to poor flowproperties. Various techniques are used today to help recover low APIoil including CO₂, steam and water injection. In drilling for oil, thenatural gas from the well is often used to re-pressurize the well inorder to enhance oil recovery. Natural gas injection, however, may dolittle to help recover low API oil that is difficult to move in the wellspace.

The disclosed system and method may be used in the recovery of petroleumcrude oil from oil wells, and may be particularly useful for enhancingrecovery of oil (e.g., heavy oil) downhole. Methane gas may be convertedto liquids in situ at a well site via the disclosed system and methodsand used for enhanced oil recovery.

In an embodiment according to this disclosure, natural gas (comprisingmethane) either from a well head or otherwise available is converted bythe disclosed system and method into liquids that are injected into thewell to enhance the recovery of heavier oil deposits therein.

In embodiments, organic oxygenates and other liquid product producedfrom gas comprising methane and exiting system 100 in line 16 and/or 24is utilized for enhanced oil recovery. System 100 may be assembled onmobile skid mounted units. Such units may permit gas conversion atremote locations, and excess gas may be flared. Larger units may be usedwhere larger deposits of heavy crude are to be recovered.

Conversion of Light Gas.

In embodiments, greater than about 80% of the light gas is convertedinto product via the disclosed method, and any remaining unconvertedlight gas is present in the reactor headspace and/or is dissolved in theliquid product. In some embodiments, greater than about 90% of the lightgas is converted into organic product. In some embodiments,substantially all of the light gas is converted to product. Inembodiments, substantially all of the light gas is converted intoproduct via multi-pass operation of a closed loop system.

In some embodiments, light gas comprises carbon dioxide, and theconversion of carbon dioxide is greater than about 60%. In embodiments,light gas comprises carbon dioxide and the conversion of carbon dioxide,is greater than about 80%. In embodiments, light gas comprises carbondioxide and the conversion of carbon dioxide, is greater than about 90%.In embodiments, a closed loop system is used, and substantially all ofthe carbon dioxide fed in dispersible gas via lines 22 and/or 23 isconverted to product.

In embodiments, light gas comprises methane and the conversion ofmethane, is greater than about 60%. In embodiments, light gas comprisesmethane and the conversion of methane, is greater than about 80%. Inembodiments, light gas comprises methane and the conversion of methane,is greater than about 90%. In embodiments, a closed loop system is used,and substantially all of the methane fed into high shear system 100 isconverted to product. In certain embodiments, the yield of organicoxygenates is greater than that of hydrocarbon. In embodiments, theyield of organic oxygenates is greater than about 50%. In someembodiments, the yield of oxygenates is greater than about 70%.

Features.

The increased surface area of the micrometer sized and/or submicrometersized light gas bubbles in the dispersion in line 18 produced withinhigh shear device 40 results in faster and/or more complete conversionof light gas. As mentioned hereinabove, additional benefits are theability to operate vessel 10 at lower temperatures and pressuresresulting in both operating and capital cost savings. The benefits ofthe present invention include, but are not limited to, faster cycletimes, increased throughput, reduced operating costs and/or reducedcapital expense due to the possibility of designing smaller reactors,and/or operating the reactor at lower temperature and/or pressure andthe possible reduction in catalyst.

The application of enhanced mixing of the reactants by HSD 40potentially permits significant production of organic product from lightgas. In some embodiments, the enhanced mixing potentiates an increase inthroughput of the process stream. In some embodiments, the high shearmixing device is incorporated into an established process, therebyenabling an increase in production (i.e., greater throughput). Incontrast to some methods that attempt to increase the degree ofconversion by simply increasing reactor pressures, the superiordispersion and contact provided by external high shear mixing may allowin many cases a decrease in overall operating pressure while maintainingor even increasing product production.

Without wishing to be limited to a particular theory, it is believedthat the level or degree of high shear mixing is sufficient to increaserates of mass transfer and also produces localized non-ideal conditionsthat permit reactions to occur that would not otherwise be expected tooccur based on Gibbs free energy predictions. Localized non idealconditions are believed to occur within the high shear device resultingin increased temperatures and pressures with the most significantincrease believed to be in localized pressures. The increase inpressures and temperatures within the high shear device areinstantaneous and localized and quickly revert back to bulk or averagesystem conditions once exiting the high shear device. In some cases, thehigh shear mixing device induces cavitation of sufficient intensity todissociate one or more of the reactants into free radicals, which mayintensify a chemical reaction or allow a reaction to take place at lessstringent conditions than might otherwise be required. Cavitation mayalso increase rates of transport processes by producing local turbulenceand liquid micro-circulation (acoustic streaming). An overview of theapplication of cavitation phenomenon in chemical/physical processingapplications is provided by Gogate et al., “Cavitation: A technology onthe horizon,” Current Science 91 (No. 1): 35-46 (2006). Under suchnon-ideal conditions, carbon dioxide and/or alkane may be dissociated;and water and/or simple alkane molecules converted into free radicals.The free radicals are then allowed to reform into hydrocarbons andoxygenates. In HSD 40, alkane is dehydrogenated and/or carbon dioxidedecoupled potentially with the aid of at least one suitable catalyst toform reactive radical compounds. The disclosed system and method mayprovide for substantially emissions-free conversion of light gas tovaluable product(s) by conversion under non-ideal conditions provided bythe use of high shear.

In some embodiments, the system and methods described herein permitdesign of a smaller and/or less capital intensive process thanpreviously possible without the use of external high shear device 40.Potential advantages of certain embodiments of the disclosed methods arereduced operating costs and increased production from an existingprocess.

Representative data obtained via an embodiment of the disclosed systemand method is presented as Examples 1-5 hereinbelow.

Fischer-Tropsch (FT) Conversion

Fischer-Tropsch (FT) process is utilized for the conversion ofcarbonaceous feedstock, e.g., coal or natural gas, to higher valueliquid fuel or petrochemicals. Large quantities of methane, the maincomponent of natural gas, are available in many areas of the world.Methane may be reformed with water or partially oxidized with oxygen toproduce carbon monoxide and hydrogen (i.e., syngas or synthesis gas).Coal and other solid materials may also be used as starting rawmaterials from which synthesis gas may be produced. In this disclosure,FT process encompasses syngas reforming (production of hydrocarbons fromcarbon monoxide and hydrogen); it also encompasses the process ofconverting natural gas or coal into liquid fuels, e.g., syngasproduction and syngas reforming.

Preparation of hydrocarbons from synthesis gas is well known in the artand is usually referred to as Fischer-Tropsch synthesis, theFischer-Tropsch process, or Fischer-Tropsch reaction(s). Catalysts foruse in such synthesis usually contain a catalytically active metal ofGroups 8, 9, 10 (in the new notation for the periodic table of theelements). In particular, iron, cobalt, nickel, and ruthenium may beused as the catalytically active metal. Cobalt and ruthenium have beenfound to be especially suitable for catalyzing a process in whichsynthesis gas is converted to primarily hydrocarbons having five or morecarbon atoms (i.e., where the C₅ ⁺ selectivity of the catalyst is high).A Fischer-Tropsch catalyst may also be promoted with other metals.

Catalytic hydrogenation of carbon monoxide by Fischer-Tropsch mayproduce a variety of products ranging from methane to higher alkanes andaliphatic alcohols. Fischer-Tropsch synthesis reactions are veryexothermic and reaction vessels must be designed for adequate heatexchange capacity. Because the reactants for Fischer-Tropsch are gaseswhile the product streams include liquids and waxes, the system istypically designed to continuously produce and remove therefrom adesired range of liquid and wax hydrocarbon products.

Research continues on developing more efficient Fischer-Tropsch catalystsystems and reaction systems that increase the selectivity forhigher-value hydrocarbons in the Fischer-Tropsch product stream. Inparticular, a number of studies describe the behavior of iron, cobalt orruthenium based catalysts in various reactor types, together with thedevelopment of catalyst compositions and preparations.

There are significant differences in the molecular weight distributionsof the hydrocarbon products from Fischer-Tropsch reaction systems.Product distribution and/or product selectivity depends on the type andstructure of the catalysts and on the reactor type and operatingconditions. In general, however, the Fischer-Tropsch process yields anabundance of higher molecular weight wax-like compounds. Lowertemperature Fischer-Tropsch operation generally produces heavierhydrocarbon products. In conventional Fischer-Tropsch processes, thehigher molecular weight materials are subsequently cracked to lowermolecular weight liquids for use as fuels and chemical feedstocks.Therefore, it is desirable to maximize the selectivity of theFischer-Tropsch synthesis to the production of high-value liquidhydrocarbons, for example hydrocarbons with five or more carbon atomsper hydrocarbon chain.

High shear systems and methods for Fischer Tropsch conversion ofsynthesis gas to liquid and gaseous hydrocarbons are disclosed. Inaccordance with certain embodiments, provided is a method for formingC2+ hydrocarbons, the method comprising forming a dispersion comprisingsynthesis gas bubbles dispersed in a liquid phase comprisinghydrocarbons in a high shear device, wherein the average bubble diameterof the synthesis gas bubbles is less than about 1.5 μm, introducing thedispersion into a reactor, and removing a product stream comprisingliquid hydrocarbons from the reactor. The gas bubbles may have a meandiameter of less than 400 nm. The gas bubbles may have a mean diameterof no more than 100 nm. The synthesis gas may be generated via naturalgas reforming. The synthesis gas may be generated via solidsgasification. In embodiments, the solid is selected from the groupconsisting of coal, biomass, and bio-renewables. The reactor maycomprise Fischer-Tropsch catalyst and the method may further comprisecirculating at least a portion of the product stream to the high sheardevice. The portion of the product stream circulated to the high sheardevice may comprise Fischer-Tropsch catalyst. The portion of the productstream circulated to the high shear device may be substantiallycatalyst-free.

In some embodiments, forming the dispersion comprises subjecting amixture of the synthesis gas and the liquid phase to a shear rate ofgreater than about 20,000 s⁻¹. The high shear device may comprise atleast one rotor, wherein the at least one rotor is rotated at a tipspeed of at least 22.9 m/s (4,500 ft/min) during formation of thedispersion. In embodiments, the high shear device produces a localpressure of at least about 1034.2 MPa (150,000 psi) at the tip of the atleast one rotor. The energy expenditure of the high shear device may begreater than 1000 W/m³. In embodiments of the method, the catalystcomprises a metal selected from the group consisting of iron, cobalt,and combinations thereof.

Also disclosed herein is a method for converting synthesis gas to C2+hydrocarbons, the method comprising forming a fluid mixture comprisingsynthesis gas and a liquid comprising hydrocarbons, subjecting the fluidmixture to a shear rate greater than 20,000 s⁻¹ to produce a dispersionof carbon monoxide and hydrogen gas bubbles in a continuous phase of theliquid, and introducing the dispersion into a Fischer-Tropsch reactorfrom which a reactor product is removed. The method may further compriseremoving a gas stream comprising unreacted synthesis gas from a topportion of the reactor, and forming additional dispersion with at leasta portion of the unreacted synthesis gas. The average bubble diameter ofthe hydrogen and carbon monoxide gas bubbles in the dispersion may beless than about 5 μm. In embodiments, the dispersion is stable for atleast about 15 minutes at atmospheric pressure. Subjecting the fluidmixture to a shear rate greater than 20,000 s⁻¹ may comprise introducingthe fluid into a high shear device comprising at least two generators.

A system for converting carbon monoxide gas and hydrogen gas into C2+hydrocarbons is disclosed herein, the system comprising at least onehigh shear mixing device comprising at least one rotor and at least onestator separated by a shear gap, wherein the shear gap is the minimumdistance between the at least one rotor and the at least stator, andwherein the high shear mixing device is capable of producing a tip speedof the at least one rotor of greater than 22.9 m/s (4,500 ft/min), and apump configured for delivering a fluid stream comprising liquid mediumto the high shear mixing device. The system may further comprise aFischer Tropsch reactor fluidly connected to an outlet of the externalhigh shear device and having an outlet for a product stream comprisingliquid hydrocarbons. The at least one high shear mixing device may beconfigured for producing a dispersion of hydrogen and carbon monoxidegas bubbles in a liquid phase, wherein the dispersion has a mean bubblediameter of less than 5 nm. In embodiments, the at least one high shearmixing device is capable of producing a tip speed of the at least onerotor of at least 20.3 m/s (4000 ft/min). The system may comprise atleast two high shear mixing devices. The reactor may be a slurryreactor. In embodiments, the system further comprises a separator, theproduct stream further comprises catalyst, and the separator comprisesan inlet connected to the outlet for the product stream and an outletfor a catalyst slurry stream from which at least a portion of the liquidhydrocarbons have been removed, and an outlet for a stream comprisingliquid hydrocarbons. The method may further comprise a recycle lineconnecting the outlet for the catalyst slurry stream and an inlet to theFischer-Tropsch reactor.

In a system for converting synthesis gas to C2+ hydrocarbons, includinga Fischer Tropsch reactor and a Fischer-Tropsch catalyst that catalyzesthe conversion of synthesis gas to hydrocarbons, an improvement isdisclosed, the improvement comprising an external high shear deviceupstream of the reactor, the external high shear device comprising aninlet for a fluid stream comprising synthesis gas and a liquid medium,and at least one generator comprising a rotor and a stator having ashear gap therebetween, wherein the high shear device provides an energyexpenditure of greater than 1000 W/m³ of fluid. The high shear devicemay comprise at least two generators. In embodiments, the shear rateprovided by one generator is greater than the shear rate provided byanother generator.

In some embodiments, the system further comprises a pump configured fordelivering a liquid medium and synthesis gas to the high shear mixingdevice. The system comprises a reactor configured for receiving adispersion from the high shear device. Some embodiments of the systempotentially make possible the conversion of synthesis gas intohydrocarbons without the need for large volume Fischer-Tropsch reactors,via the use of an external pressurized high shear reactor.

Overview.

The rate of chemical reactions involving liquids, gases and solidsdepend on time of contact, temperature, and pressure. In cases where itis desirable to react two or more raw materials of different phases(e.g. solid and liquid; liquid and gas; solid, liquid and gas), one ofthe limiting factors controlling the rate of reaction involves thecontact time of the reactants. In the case of heterogeneously catalyzedreactions there is the additional rate limiting factor of having thereacted products removed from the surface of the catalyst to permit thecatalyst to catalyze further reactants. Contact time for the reactantsand/or catalyst is often controlled by mixing which provides contactwith two or more reactants involved in a chemical reaction.

A reactor assembly that comprises an external high shear device or mixeras described herein makes possible decreased mass transfer limitationsand thereby allows the reaction to more closely approach kineticlimitations. When reaction rates are accelerated, residence times may bedecreased, thereby increasing obtainable throughput. Product yield maybe increased as a result of the high shear system and process.Alternatively, if the product yield of an existing process isacceptable, decreasing the required residence time by incorporation ofsuitable high shear may allow for the use of lower temperatures and/orpressures than conventional processes. Lower temperature Fischer-Tropschconversion may be used to desirably produce heavier hydrocarbons.

Furthermore, without wishing to be limited by theory, it is believedthat the high shear conditions provided by a reactor assembly thatcomprises an external high shear device or mixer as described herein maypermit Fischer-Tropsch conversion of synthesis gas into liquidhydrocarbons generally having five or more carbon atoms (C5+hydrocarbons) and gaseous hydrocarbons generally having two or morecarbon atoms (C2+ hydrocarbons) at global operating conditions underwhich reaction may not conventionally be expected to occur to anysignificant extent.

System for Fischer-Tropsch Conversion of Synthesis Gas to Hydrocarbons.

A high shear Fischer-Tropsch conversion system will now be described inrelation to FIG. 3, which is a process flow diagram of an embodiment ofa high shear system 100 for conversion of synthesis gas intohydrocarbons. The basic components of a representative system includeexternal high shear mixing device (HSD) 40, reactor 10, and pump 5. Asshown in FIG. 3, high shear device 40 is located external to reactor 10.Each of these components is further described in more detail below. Line21 is connected to pump 5 for introducing liquid medium into HSD 40.Line 13 connects pump 5 to HSD 40, and line 18 connects HSD 40 toreactor 10. Line 22 may be connected to line 13 for introducing a gascomprising carbon monoxide and hydrogen (i.e., synthesis gas).Alternatively, line 22 may be connected directly to HSD 40. Line 17 maybe connected to reactor 10 for removal of unreacted carbon monoxide,hydrogen and/or other input gas or product gaseous C2+ hydrocarbons. Inapplications, line 17 may be fluidly connected to line 22 whereby aportion of the gas in line 17 may be recycled to HSD 40. Additionalcomponents or process steps may be incorporated between reactor 10 andHSD 40, or ahead of pump 5 or HSD 40, if desired, as will becomeapparent upon reading the description of the high shear Fischer-Tropschprocess described hereinbelow. For example, as indicated in FIG. 3, heattransfer devices such as heat transfer devices 60 and 80 may bepositioned throughout system 100 for removing the heat produced duringexothermic Fischer-Tropsch conversion. Line 16 may be connected to line21 or line 13 (e.g., from reactor 10), to provide for multi-passoperation, if desired. As shown in FIG. 3, for example, line 20 mayconnect line 16 to line 21.

In cases where Fischer-Tropsch catalyst is circulated through HSD 40(e.g., when reactor 10 is operated as a circulated slurry loop reactor),high shear Fischer-Tropsch system 100 may further comprise separator 30.Separator 30 may be connected to reactor 10 via lines 16 and 45. Productfrom reactor 10 may be introduced to separator 30 via line 16. Line 45may connect separator 30 to reactor 10 for return of catalyst slurry toreactor 10.

High shear Fischer-Tropsch system 100 may further comprise downstreamprocessing units for upgrading the liquid and gaseous products fromreactor 10 (not shown in FIG. 3).

High Shear Mixing Device.

External high shear mixing device (HSD) 40, also sometimes referred toas a high shear device or high shear mixing device, is configured forreceiving an inlet stream, via line 13, comprising liquid medium andsynthesis gas. Alternatively, HSD 40 may be configured for receiving theliquid medium and synthesis gas streams via separate inlet lines (notshown). Although only one high shear device is shown in FIG. 3, itshould be understood that some embodiments of the system may have two ormore high shear mixing devices arranged either in series or parallelflow.

The product dispersion comprising synthesis gas bubbles, and optionallycatalyst particles, in a continuous liquid phase may be referred to asan emulsion. The product dispersion has an average gas bubble size lessthan about 5 μm. In embodiments, HSD 40 produces a dispersion having amean bubble size of less than about 1.5 μm. In embodiments, HSD 40produces a dispersion having a mean bubble size of less than 1 μm;preferably the bubbles are sub-micron in diameter. In certain instances,the average bubble size is from about 0.1 μm to about 1.0 μm. Inembodiments, HSD 40 produces a dispersion having a mean bubble size ofless than 400 nm. In embodiments, HSD 40 produces a dispersion having amean bubble size of less than 100 nm. High shear device 200 produces adispersion comprising gas bubbles capable of remaining dispersed atatmospheric pressure for at least about 15 minutes.

Reactor 10.

The Fischer-Tropsch reaction is a heterogeneous catalytic reactioninvolving a solid catalyst, gaseous carbon monoxide and hydrogenreactants, and liquid product. Reactor 10 may be any type of reactor inwhich Fischer-Tropsch reaction may be carried out. For instance, acontinuous or semi-continuous stirred tank reactor, or one or more batchreactors may be employed in series or in parallel. In embodiments,reactor 10 comprises one or more tank or tubular reactor in series or inparallel. Fischer-Tropsch reactor 10 may be operated as a multitubularfixed bed reactor, a fixed slurry bed reactor, a fixed fluidized bedreactor, or a circulating fluidized bed reactor as known to those ofskill in the art.

Any number of reactor inlet lines is envisioned, with three shown inFIG. 3 (lines 15, 18 and 45). Line 18 provides the dispersion ofreactant gas comprising carbon monoxide and hydrogen to reactor 10. Line18 may introduce the dispersion into the bottom half of reactor 10,alternatively, the bottom 25% of reactor 10. Inlet line 15 may beconnected to reactor 10 for receiving a catalyst solution or slurryduring operation and/or during initiation of the system. When reactor 10is operated as a circulating slurry reactor, inlet line 45 may beconnected with separator 30 for introducing concentrated catalyst slurryfrom which liquid product has been removed to reactor 10. Reactor 10 maycomprise exit line 17 for extracting gas from the top portion of reactor10. Line 16 is connected to a bottom portion of reactor 10 for removingliquid product from reactor 10. In embodiments where a fixed bed ofcatalyst is utilized, i.e. where reactor 10 is a multi-tubular fixedbed, a fixed fluidized bed, or a fixed slurry bed, outlet line 16 maycomprise no catalyst, and a separator may serve to separate liquidmedium from the product hydrocarbons, or separator 30 may be absent insome applications. It is envisaged that reactor 10 may comprise aplurality of reactor product lines 16.

Fischer-Tropsch conversion will occur whenever suitable time,temperature and pressure conditions exist. In this sense synthesis gasconversion could occur at any point in the flow diagram of FIG. 3 iftemperature and pressure conditions are suitable. Where a circulatingslurry-based catalyst is utilized (i.e., when line 21 contains catalystparticles), reaction is more likely to occur at points outside reactor10 shown of FIG. 3, than when catalyst is constrained to reactor 10.Nonetheless a discrete reactor 10 is often desirable to allow forincreased residence time, agitation and heating and/or cooling.

Reactor 10 may include one or more of the following components: stirringsystem, temperature control system, pressure measurementinstrumentation, temperature measurement instrumentation, one or moreinjection points, and level regulator (not shown), as are known in theart of reaction vessel design. For example, a stirring system mayinclude a motor driven mixer. A temperature control system may comprise,for example, a heat exchanger 70 with cooling coils or heat transfertubes. Alternatively, as much of the conversion reaction may occurwithin HSD 40 in some embodiments, reactor 10 may serve primarily as astorage vessel in some cases. Although generally less desired, in someapplications reactor 10 may be omitted, particularly if multiple highshear devices 40 are employed in series, as further described below.

Separator 30.

Separator 30 may be any apparatus suitable for separating a concentratedcatalyst slurry from the liquid hydrocarbon products produced in system100 and any liquid medium charged to the system. Separator 30 may be,for example, selected from hydrocyclones, gravity separators, filters,and magnetic separators. In some embodiments, separator 30 may be adistillation column, whereby liquid hydrocarbons and liquid charge maybe separated from Fischer-Tropsch catalyst. In embodiments where gas isremoved with liquid hydrocarbon product in line 16, an additionalseparator may serve to separate gaseous product and unreacted carbonmonoxide and hydrogen from liquid hydrocarbon product and liquid medium.Unreacted carbon monoxide and hydrogen may be separated from low-boilinggaseous hydrocarbon and recycled to HSD 40. If the product in line 16comprises catalyst, the separated liquid hydrocarbon product may then beintroduced into separator 30 for removal of a concentrated catalyststream from the liquid hydrocarbon product.

Heat Transfer Devices.

In addition to the above-mentioned heating/cooling capabilities ofreactor 10, other external or internal heat transfer devices for heatingor cooling a process stream are also contemplated in variations of theembodiments illustrated in FIG. 3. As Fischer-Tropsch conversion ishighly exothermic, heat may be removed from reactor 10 via any methodknown to one skilled in the art. For example, reactor 10 may compriseone or more internal heat transfer devices 70. The use of externalheating and/or cooling heat transfer devices is also contemplated. Somesuitable locations for one or more such heat transfer devices arebetween pump 5 and HSD 40, between HSD 40 and reactor 10, and upstreamof pump 5. In the embodiment of FIG. 3, heat transfer device 60 ispositioned on gas recycle line 50. In embodiments, heat transfer device60 is a condenser. The embodiment of FIG. 3 also comprises a heattransfer device 80 positioned on line 21. Heat transfer device 80 maybe, for example, a condenser. Some non-limiting examples of such heattransfer devices are condensers, and shell, tube, plate, and coil heatexchangers, as are known in the art.

Pumps.

Pump 5 is configured for either continuous or semi-continuous operation.The capabilities and configuration of pump 5 are described herein above.In addition to pump 5, one or more additional, high pressure pump (notshown) may be included in the system illustrated in FIG. 3. For example,a booster pump, which may be similar to pump 5, may be included betweenHSD 40 and reactor 10 for boosting the pressure into reactor 10. Such abooster pump may be capable of pressures of from about 500 kPa (72.5psi) to about 1500 kPa (725 psi), from about 1500 kPa (218 psi) to about3500 kPa (508 psi), or from about 2000 kPa (290 psi) to about 3000 kPa(435 psi). As another example, a supplemental feed pump, which may besimilar to pump 5, may be included for introducing additional reactantsor catalyst into reactor 10, for example, via line 15.

Production of Hydrocarbons by Fischer-Tropsch Conversion of SynthesisGas.

Operation of high shear synthesis gas conversion system 100 will now bediscussed with reference to FIG. 3. The system is initially charged witha suitable liquid medium within which the Fischer-Tropsch reactant gaseswill be dispersed. The initial liquid medium charge may be a variety oftypes. Suitable hydrocarbon liquids include any aliphatic or aromaticlow viscosity organic liquid. Any inert carrier such as silicone oil mayalso be utilized. Other fluids such as water may also be utilized;however, the resulting dissociation of water may cause co-products ofalcohols and aldehydes to be formed. In general the presence of anysource of oxygen is undesirable due to the possible oxidation of CO toCO₂. Selection of the liquid will be dependent on the desired reactionproducts from the Fischer-Tropsch process and their solubility in theselected organic liquid. Desirably, the initial charge of liquid mediumcomprises one or more liquid hydrocarbon product produced by theFischer-Tropsch reaction such that no separation is needed to separateliquid hydrocarbon products produced in high shear system 100 from theinitial charge of liquid medium.

Dispersible gas line 22 comprises synthesis gas to be converted viaFischer Tropsch conversion to C2+ hydrocarbons. The synthesis gas may beprepared or obtained using any method known in the art, includingpartial oxidation of hydrocarbons, steam reforming, and autothermalreforming. The length of the hydrocarbon chain produced viaFischer-Tropsch conversion is affected by the composition (or ratio ofhydrogen to carbon monoxide) of the synthesis gas, the reactionconditions, and the catalyst selectivity. In embodiments, the H₂:COratio of the dispersible synthesis gas stream introduced via line 22 isfrom about 1:1 to about 5:1. In embodiments, the H₂:CO ratio of thedispersible synthesis gas stream introduced via line 22 is from about1.7:1 to about 3:1. In embodiments, the H₂:CO ratio is about 2.Typically, synthesis gas is produced via gas reformation or gasificationof solids, depending on the raw material or feedstock available. Inembodiments, carbon monoxide and hydrogen gas in dispersible line 22 isproduced via reforming or partial oxidation of natural gas. Inembodiments, synthesis gas in line 22 is obtained via gasification of asolid material such as, but not limited to, coal, biomass, andbio-renewables.

In embodiments, the dispersible gas is fed directly into HSD 40, insteadof being combined with the liquid reactant stream (i.e., liquid medium)in line 13. Pump 5 may be operated to pump the liquid stream (which willcomprise liquid medium and may also comprise product hydrocarbons formultiple cycle operation and which may comprise product hydrocarbons andcatalyst, for circulated slurry operation) through line 21, and to buildpressure and feed HSD 40, providing a controlled flow throughout HSD 40and high shear system 100. In some embodiments, pump 5 increases thepressure of the HSD inlet stream to greater than 200 kPa (29 psi),greater than about 300 kPa (43.5 psi), greater than about 500 kPa (72.5psi), greater than about 1000 kPa (145 psi), or greater than 1500 kPa(218 psi). In this way, high shear system 100 may combine high shearwith pressure to enhance reactant intimate mixing.

A heat exchange device may be positioned on line 21 or line 13 forcooling the liquid medium. In the embodiment of FIG. 3, heat exchangedevice 80 is positioned on line 21.

After pumping, the dispersible gas from line 22 and the liquid from line13 are mixed within HSD 40, which serves to create a fine dispersion ofthe carbon monoxide and hydrogen gas in the liquid. In enclosed,external, HSD 40, the synthesis gas and the liquid are highly dispersedsuch that nanobubbles, submicron bubbles, and/or microbubbles of thegaseous reactants in liquid medium are formed for superior dissolutioninto solution and enhancement of reactant mixing. For example, disperserIKA® model DR 2000/4, a high shear, three stage dispersing deviceconfigured with three rotors in combination with stators, aligned inseries, may be used to create the dispersion of dispersible carbonmonoxide and hydrogen gas reactants in liquid medium comprisinghydrocarbons. The rotor/stator sets may be configured as illustrated inFIG. 2, for example. The dispersed reactants enter the high shear devicevia line 13 and enter a first stage rotor/stator combination. The rotorsand stators of the first stage may have circumferentially spaced firststage rotor teeth and stator teeth, respectively. The coarse dispersionexiting the first stage enters the second rotor/stator stage. The rotorand stator of the second stage may also comprise circumferentiallyspaced rotor teeth and stator teeth, respectively. The reducedbubble-size dispersion emerging from the second stage enters the thirdstage rotor/stator combination, which may comprise a rotor and a statorhaving rotor teeth and stator teeth, respectively. The dispersion exitsthe high shear device via line 18. The dispersion may further catalystparticles in embodiments in which catalyst is circulated through HSD 40.In some embodiments, the shear rate increases stepwise longitudinallyalong the direction of the flow, 260.

For example, in some embodiments, the shear rate in the firstrotor/stator stage is greater than the shear rate in subsequentstage(s). In other embodiments, the shear rate is substantially constantalong the direction of the flow, with the shear rate in each stage beingsubstantially the same.

If the high shear device 40 includes a PTFE seal, the seal may be cooledusing any suitable technique that is known in the art. For example,fresh catalyst slurry or optional injected low-boiling hydrocarbonstreams (not shown in FIG. 3) may be used to cool the seal and in sodoing be preheated as desired prior to entering high shear system 100,for example before entering high shear device 40.

The rotor(s) of HSD 40 may be set to rotate at a speed commensurate withthe diameter of the rotor and the desired tip speed. As described above,the high shear device (e.g., colloid mill or toothed rim disperser) haseither a fixed clearance between the stator and rotor or has adjustableclearance. HSD 40 serves to intimately mix the synthesis gas and theliquid medium (i.e., fluid stream in line 13 comprising liquid medium,and optionally comprising product hydrocarbons and/or catalyst). In someembodiments of the process, the transport resistance of the reactants isreduced by operation of the high shear device such that the velocity ofthe reaction is increased by greater than about 5%. In some embodimentsof the process, the transport resistance of the reactants is reduced byoperation of the high shear device such that the velocity of thereaction is increased by greater than a factor of about 5. In someembodiments, the velocity of the reaction is increased by at least afactor of 10. In some embodiments, the velocity is increased by a factorin the range of about 10 to about 100 fold.

Once dispersed, the resulting gas/liquid or gas/liquid/solid dispersionexits HSD 40 via line 18 and feeds into reactor 10, as illustrated inFIG. 3. Optionally, the dispersion may be further processed (e.g.,cooled) prior to entering reactor 10, if desired. In reactor 10,Fischer-Tropsch conversion occurs/continues via contact withFischer-Tropsch catalyst.

In embodiments, liquid medium, and catalyst are first mixed in reactor10. Liquid medium and catalyst may enter reactor 10 as a slurry via, forexample, inlet line 15. Any number of reactor inlet lines is envisioned,with three shown in FIG. 3 (lines 15, 18 and 45). In an embodiment,reactor 10 is charged with catalyst and the catalyst if required, isactivated according to procedures recommended by the catalyst vendor(s),prior to introduction of dispersible gas comprising carbon monoxide andhydrogen into HSD 40.

In embodiments, as shown in FIG. 3, reactor 10 catalyst slurry iscirculated through HSD 40. In such embodiments, product in line 16comprises catalyst, along with liquid product hydrocarbons, and liquidmedium (which was used during start-up, for example). In someembodiments, reactor 10 comprises a fixed catalyst bed (e.g., a fixedslurry bed), and catalyst is not removed with liquid product in line 16and catalyst is not circulated through HSD 40. In fixed catalystembodiments, wherein catalyst is not circulated through HSD 40, productin line 16 comprises product hydrocarbon and liquid medium. Such productmay be sent directly for further processing, or may be recycled, vialine 21 for example, to HSD 40 for multi-pass operation.

In the embodiment of FIG. 3, gas stream is removed via line 17 from agas cap above the level 75 of catalyst suspension or catalyst bed withinreactor 10. In other instances, unreacted synthesis gas and productgases (e.g., hydrocarbons with less than 6 carbons) are removed fromreactor 10 via line 16 as a mixed stream with liquid hydrocarbonproduct. In such applications, gaseous and liquid hydrocarbon productsmay be separated from unreacted carbon monoxide and hydrogen gas inapparatus external to reactor 10. In such embodiments, product removedvia line 16 may comprise gaseous hydrocarbon product and unreactedreactant synthesis gas in addition to liquid hydrocarbon product andoptionally catalyst. As mentioned above, in such instances, a separator(not shown) may be used to separate unreacted synthesis gas for recycleto HSD 40.

As a result of the intimate mixing of the gaseous reactants prior toentering reactor 10, a significant portion of the chemical reaction maytake place in HSD 40, when catalyst is circulated throughout system 100.Accordingly, in some embodiments, reactor 10 may be used primarily forheating/cooling and separation of product hydrocarbons from unreactedreactant and product gases. Alternatively, or additionally, reactor 10may serve as a primary reaction vessel, especially in cases wherecatalyst is not circulated throughout system 100 but is associated withreactor 10, where most of the product hydrocarbon is produced. Forexample, in embodiments, reactor 10 is a fixed bed reactor (e.g., afixed fluidized bed reactor, a fixed slurry bed reactor, or amulti-tubular fixed bed reactor) comprising catalyst, and the catalystis not circulated through HSD 40. In such embodiments, although catalystmay not circulate through HSD 40, catalyst (or slurry) may still beadded to or removed from reactor 10 or may be looped about reactor 10.That is, although in some embodiments catalyst is not circulated throughHSD 40, catalyst may still be circulated internally within reactor 10 ormay be looped, introduced, or removed from reactor 10.

Reactor 10 may be operated in either continuous or semi-continuous flowmode, or it may be operated in batch mode. The contents of reactor 10may be maintained at a specified reaction temperature using heatingand/or cooling capabilities (e.g., cooling coils) and temperaturemeasurement instrumentation. As Fischer-Tropsch is highly exothermic,reactor 10 may comprise an internal heat exchanger 70. Internal heatexchanger 70 may be, for example, one or more cooling coils/heattransfer tubes positioned within reactor 10. Pressure in reactor 10 maybe monitored using suitable pressure measurement instrumentation, andthe level of catalyst suspension in reactor 10 may be controlled using alevel regulator (not shown), employing techniques that are known tothose of skill in the art. The contents may be stirred continuously orsemi-continuously.

Catalyst.

High shear system 100 comprises a suitable Fischer-Tropsch catalyst, asknown in the art. In embodiments, the catalyst is circulated throughoutthe system, via lines 16, 21, 13, and 18. In other embodiments, a fixedcatalyst is utilized, and the catalyst remains within reactor 10. In anyevent, a suitable Fischer-Tropsch catalyst is utilized. For example, theFischer-Tropsch catalyst may comprise a supported or unsupported Group8, 9, or 10 metal. In embodiments, the Group VIII metal is selected formiron, cobalt, ruthenium, nickel, and combinations thereof. The activityof nickel and ruthenium catalysts is conventionally not great enough forcommercial use and the price of ruthenium often makes it an unattractiveoption. Typically, iron is much less costly, while cobalt has theadvantage of higher activity and longer life. Because the incorporationof high shear may permit operation at lower temperature and moreeffective catalyst utilization, the disclosed system and method may makethe use of ruthenium and nickel more attractive. The catalyst metal maybe supported on an inorganic refractory oxide, such as alumina, silica,silica-alumina, titania, zinc oxide, and Group 4 oxides. The catalystmay further comprise a promoter metal selected from ruthenium, platinum,palladium, rhenium, cerium, halfnium, zirconium, lanthanum, copper andcombinations thereof.

Suitable Fischer-Tropsch catalyst may be introduced into reactor 10 vialine 15, as a slurry of catalyst in liquid medium or as a catalyststream. In some embodiments, the catalyst is added continuously toreactor 10 via line 15. In embodiments, reactor 10 comprises a fixed bedof suitable catalyst. In embodiments, catalyst is introduced intoreactor 10 and activated according to manufacturer's protocol prior toinitiating synthesis gas conversion. Alternatively, or additionally,fresh catalyst may be added elsewhere in high shear Fischer-Tropschsystem 100. For example, fresh catalyst slurry may be injected into line21 or into line 45. Spent catalyst may be removed from system 100 andreplaced with fresh catalyst as needed. For example, a portion ofcatalyst in line 45 may be removed and new catalyst introduced intoreactor 10, for example via line 15. Thus, in some embodiments, line 21comprises hydrocarbon product, liquid medium (which may be hydrocarbonproduct) and catalyst, and in other embodiments, line 21 carries a fluidstream comprising hydrocarbon product and liquid medium, with nocatalyst.

Synthesis gas in dispersible gas line 22 is converted into gaseous andliquid hydrocarbons (e.g., olefins, paraffins, and oxygenated products)via contact with a Fischer-Tropsch catalyst. The Fischer-Tropsch processmay be performed either as a high temperature Fischer-Tropsch (HTFT)process, or, perhaps more desirably, a low temperature Fischer-Tropsch(LTFT) process. In embodiments, the Fischer-Tropsch conversion isoperated as a LTFT process, and the operating temperature is in therange of from about 180° C. to about 240° C. In embodiments, theFischer-Tropsch conversion is operated as a HTFT process, and thetemperature is in the range of from about 300° C. to 350° C. Inembodiments, HTFT is selected, and the catalyst comprises iron. Inembodiments, LTFT is selected, and the catalyst comprises iron orcobalt. In embodiments, the temperature of reactor 10 is maintained inthe range of from about 180° C. to about 280° C., alternatively, in therange of from 190° C. to 240° C.

In embodiments, the reactor 10 pressure may be from about 500 kPa (72.5psi) to about 1500 kPa (725 psi). In embodiments, the reactor 10pressure may be from about 1500 kPa (218 psi) to about 3500 kPa (508psi). In embodiments, the reactor 10 pressure may be from about 2000 kPa(290 psi) to about 3000 kPa (435 psi). In embodiments, reactor 10 isoperated at near atmospheric pressure.

Product hydrocarbons may be produced either continuously,semi-continuously or batch wise, as desired for a particularapplication. Unreacted gas and product gas may exit reactor 10 via gasline 17. This gas stream may comprise unreacted carbon monoxide andhydrogen, as well as low-boiling product hydrocarbons, vaporized water,and inert gas. The reaction gas removed via line 17 may be furthertreated, and the components may be recycled, as desired. For example, aportion of the gas in line 17 may be removed as purge. Gaseous C2+hydrocarbons (generally having less than 6 carbon atoms) may beseparated from the purge stream and recycled to high shear system 100 orsent for downstream processing. A portion of the gas in line 17 may berecycled as reactant to HSD 40 via line 50. Heat produced by theexothermic Fischer-Tropsch reaction may desirably be removed from theportion of gas in line 17 recycled to HSD 40. In embodiments,low-boiling product hydrocarbons and vaporized water may be removed fromthe reactant gas and gaseous hydrocarbons having from one to threecarbon atoms (e.g., methane, ethane, propane) by introducing the gasinto a condenser 60. The condensed liquids comprising water and lowboiling hydrocarbons may thus be separated (and exit high shear system100) from a gas stream comprising carbon monoxide, hydrogen, and gaseoushydrocarbons having from one to three carbon atoms. The gas stream fromcondenser 60 may be recycled to reactor 10 via line 22. If gaseousreactants in line 22 have not been pre-cooled, line 22 may be introducedinto line 50 such that fresh gaseous reactants are cooled in heatexchanger 60.

Liquid hydrocarbon products of C5⁺ are extracted from high shearFischer-Tropsch system 100 via product outlet line 16. Product outletline 16 may be positioned within the lower 50% of reactor 10,alternatively, within the lower 20% of reactor 10. Fluid may becontinuously circulated via line 21 and the Fischer-Tropsch conversioncontinued over a time period sufficient to produce a desired hydrocarbonproduct, after which the reaction is terminated as known to those ofskill in the art. Catalyst reactivation may be accomplished by meansknown to those experienced in the art.

In embodiments, product stream in line 16 comprises producthydrocarbons, liquid medium, and catalyst. In embodiments, product inline 16 comprises product hydrocarbons and liquid medium. When acirculating catalyst slurry is utilized, hydrocarbon product streamcomprising product hydrocarbons, liquid medium, and catalyst may beintroduced into a separator 30 for separation of the product from thecatalyst. Separated concentrated catalyst slurry may be recycled toreactor 10 via, for example, line 45. Catalyst-free product may be sentfor further processing, for example, via line 35.

In embodiments, at least a portion of reactor discharge in line 16 isintroduced to line 21 pump 5 and circulated to HSD 40. In suchembodiments, heat exchange device 80 may be used to reduce thetemperature in line 21. In embodiments, reactor 10 comprises catalystslurry and a portion of slurry exits reactor 10 via line 16 and enterspump 5 via pump inlet line 21. Water may be removed from the portion ofthe reactor discharge in line 16 which is recycled to system 100, asknown in the art. Condenser 80 may be used to remove water and reactionheat from fluid in line 21. After pumping, the pressurized slurry ismixed with synthesis gas via dispersible gas line 22 in high sheardevice 40, which serves to intimately mix the reactants and catalyst. Inembodiments, the reactor 10 comprises an uncirculated bed (slurry,fixed, or fluidized) of catalyst, and line 21 comprises liquidcatalyst-free hydrocarbon stream from reactor 10 discharge line 16.

The hydrocarbon product produced via the high shear system and processmay comprise a mixture of hydrocarbons having a chain length of greaterthan 5 carbon atoms. The hydrocarbon liquid product may comprise amixture of hydrocarbons having chain lengths from 5 to about 90 carbonatoms. In embodiments, the majority of the hydrocarbons in thehydrocarbon liquid product have a chain length in the range of from 5 toabout 30 carbon atoms. Product upgrading may produce a wide range ofcommercial products, for example, gasoline, candle wax, and middledistillate fuels including diesel, naphtha, and kerosene.

Single Pass Operation.

In the embodiment shown in FIG. 3, the system is configured for multiplepass operation, wherein a portion of the output from reactor 10 isdirected back to HSD 40. In embodiments, single pass operation may bedesired. In this case, product in line 16 (for fixed catalyst bedoperation) or line 35 (for circulated catalyst operation) may bedirected directly to further processing for recovery of desiredproducts. In some embodiments it may be desirable to pass the contentsof line 16, or a liquid fraction thereof, through HSD 40 during multiplepasses, as described above. In this case, line 16 may be connected toline 21 as indicated by line 20 in FIG. 3, such that at least a portionof the contents of line 16 is recycled from reactor 10 and pumped bypump 5 into line 13 and thence into HSD 40. Additional synthesis gas maybe injected via line 22 into line 13, or it may be added directly intothe high shear device (not shown).

Multiple High Shear Mixing Devices.

In some embodiments, two or more high shear devices like HSD 40, orconfigured differently, are aligned in series, and are used to furtherenhance the reaction. Operation of serial high shear devices 40 may bein either batch or continuous mode. In some instances wherein catalystis circulated through HSD 40 via line 21, the use of multiple high sheardevices in series may permit fewer passes through the system to attain adesired product profile. For example, in embodiments, outlet dispersion18 may be fed into a second high shear device. When multiple high sheardevices 40 are operated in series, additional synthesis gas may beinjected into the inlet feedstream of each high shear device. In someembodiments, multiple high shear devices 40 are operated in parallel,and the outlet dispersions therefrom are introduced into one or morereactor 10.

Downstream Processing.

The product liquid hydrocarbons separated from product line 16 orseparated and condensed out of gas line 17 may be hydrocracked. Thehydrocracking may be catalytic hydrocracking, wherein the liquidhydrocarbon product is contacted with a hydrocracking catalyst. Suitablehydrocracking catalyst may comprise a metal selected from nickel,molybdenum, cobalt, tungsten, or a combination thereof. The catalystmetal may be supported on a support selected from silica,silica-alumina, and zeolites.

The increased surface area of the micrometer sized and/or submicrometersized synthesis gas bubbles in the dispersion in line 18 produced withinhigh shear device 40 results in faster and/or more complete reaction ofhydrogen and carbon monoxide within reactor 10 and, if circulatingcatalyst operation is chosen, throughout high shear system 100. Asmentioned hereinabove, potential benefits are the ability to operatereactor 10 at lower temperatures and pressures resulting in bothoperating and capital cost savings. Operation of Fischer-Tropsch reactor10 at lower temperature may increase production of heavier hydrocarbons.The benefits of the present invention may include, but are not limitedto, faster cycle times, increased throughput, reduced operating costsand/or reduced capital expense due to the possibility of designing asmaller Fischer-Tropsch reactor 10, operating reactor 10 at lowertemperature and/or pressure of Fischer-Tropsch conversion, and/or thepossible reduction in the amount of catalyst.

The application of enhanced mixing of the reactants by HSD 40potentially permits enhanced Fischer-Tropsch conversion of synthesisgas. In some embodiments, the enhanced mixing potentiates an increase inthroughput of the process stream. In some embodiments, the high shearmixing device is incorporated into an established process, therebyenabling an increase in production (i.e., greater throughput). Potentialadvantages of certain embodiments of the disclosed methods are reducedoperating costs and increased production from an existing process.Certain embodiments of the disclosed processes additionally offer theadvantage of reduced capital costs for the design of new processes. Inembodiments, dispersing synthesis gas in liquid medium within high sheardevice 40 decreases the amount of unreacted synthesis gas in line 17.

Without wishing to be limited to a particular theory, it is believedthat the high shear mixing device of certain embodiments of the presentsystem and methods induces cavitation whereby hydrogen and carbonmonoxide are dissociated into free radicals, which then react to produceproduct hydrocarbons.

The present methods and systems for conversion of synthesis gas into C2+hydrocarbons via Fischer-Tropsch reactions employ an external high shearmechanical device to provide rapid contact and mixing of chemicalingredients in a controlled environment in the reactor/high sheardevice. The high shear device reduces the mass transfer limitations onthe reaction and thus increases the overall reaction rate, and may allowsubstantial reaction of carbon monoxide and hydrogen under globaloperating conditions under which substantial reaction may not beexpected to occur.

In embodiments, the system and process of the present disclosure providefor a higher selectivity to C5⁺ hydrocarbons than conventionalFischer-Tropsch processes comprising an absence of external high shearmixing. In embodiments, the degree of mixing in external high sheardevice 40 is varied to attain a desired outlet product profile. ForFischer-Tropsch conversion, lowering the operating temperature increasesthe production of heavier hydrocarbons. Because Fischer-Tropschconversion is highly exothermic, it is often challenging to sufficientlycool Fischer-Tropsch reactor 10 such that longer chain hydrocarbons areproduced. A certain amount of energy (i.e., thermal energy) is requiredto initiate and maintain the Fischer-Tropsch reaction. Typically, theoperating temperature will be greater than about 180° C. In embodiments,the high shear Fischer-Tropsch process of the present disclosure allowsoperation of Fischer-Tropsch reactor 10 at a lower temperature wherebylonger hydrocarbons are produced. In embodiments, the use of the presentsystem and method for the Fischer-Tropsch production of C2+ hydrocarbonsmakes economically feasible the use of ruthenium and/or nickel catalystson a commercial scale, by increasing contact with catalyst (bydecreasing mass transfer resistance).

Gasification of Carbonaceous Materials

Synthesis gas or ‘syngas’ is a mixture of hydrogen and carbon monoxideutilized in many industrial processes. For example, synthesis gas may beburned directly in internal combustion engines, used to produce methanoland hydrogen, or converted via the Fischer-Tropsch process intosynthetic fuel.

Carbon monoxide, CO, and hydrogen, H₂ (i.e. synthesis gas), are theinitial reactants used in the Fischer-Tropsch process. The resultinghydrocarbon products are refined to produce the desired synthetic fuel.The utility of the FT process is primarily in its role in producingfluid hydrocarbons from natural gas or solid feedstock. Variousfeedstocks are utilized including natural gas, lignite, peat, coal orsolid carbon-containing wastes of various types. Non-oxidative pyrolysisof the hydrocarbon feedstock may be used to produce syngas which can beused directly as a fuel without being taken through Fischer-Tropschtransformations. If liquid petroleum-like fuel, lubricant, or wax issought, the Fischer-Tropsch conversion of synthesis gas can be utilized.

Synthesis gas is usually produced by one of two methods. Synthesis gasmay be produced by the partial combustion of a hydrocarbon, as indicatedin Eq. 1:C_(n)H_((2n+2))+½nO₂→(n+1)H₂ +nCO.  (1)

When n=1 (methane), for example, the equation becomes:CH₄+½O₂→2H₂+CO,  (2a)which may also be written as:2CH₄+O₂→4H₂+2CO.  (2b)

Synthesis gas may also be produced by the gasification (also calledsteam reforming) of carbonaceous material, such as coal, biomass, ornatural gas:CH_(x)+H₂O→(1+0.5x)H₂+CO.  (3)

The value of x depends on the type of fuel. For example, natural gas hasa greater hydrogen content (from x=4 to x˜2.5) than coal (x<1). Theenergy needed for the endothermic gasification reaction (3) is usuallyprovided by the (exothermic) combustion of the hydrocarbon source withoxygen.

Gasification is a process that converts carbonaceous materials, such ascoal, petroleum, biofuel, and biomass, into hydrogen and carbon monoxideby reacting the raw material at high temperatures with a controlledamount of oxygen and/or steam. The resulting gas mixture is calledsynthesis gas or syngas and is itself a fuel. Gasification may be usedto extract energy from a variety of organic materials.

The advantage of gasification lies in the potential that using thesyngas may be more efficient than direct combustion of the originalcarbonaceous material because it can be combusted at higher temperaturesor even in fuel cells. Gasification can also utilize materials that arenot otherwise particularly suitable as fuel, for example organic wasteor biomass. In addition, the high-temperature combustion refines outcorrosive ash elements such as chloride and potassium, providing cleangas from otherwise potentially problematic fuels.

Gasification of fossil fuels is currently widely used on industrialscales to generate electricity. However, almost any type of organicmaterial can be used as the raw material for gasification, such as wood,biomass, or even plastic waste.

Gasification relies on chemical processes at elevated temperatures(generally greater than 700° C.), which distinguishes it from biologicalprocesses such as anaerobic digestion that produce biogas.

Gasification may be carried out in a gasifier. In a gasifier, thecarbonaceous material undergoes several different processes. Thepyrolysis (or devolatilization) process occurs as the carbonaceousparticles are heated. Volatiles are released and char is produced. Thismay result in up to 70% weight loss for coal. The process is, of course,dependent on the properties of the carbonaceous material being processedwhich determines the structure and composition of the char, which willthen undergo gasification reactions.

The combustion process occurs as the volatile products and some of thechar react with oxygen to form carbon dioxide and carbon monoxide. Thecombustion process provides heat for the subsequent gasificationreactions. Letting C represent a carbon-containing organic compound, thebasic reaction here is:C+1/2O₂→CO.  (4)

The gasification process occurs as the char reacts with carbon dioxideand steam to produce carbon monoxide and hydrogen, via gasificationreaction (3), which for x approaching zero becomes:C+H₂O→H₂+CO.  (5)

In addition, the reversible gas phase water gas shift reaction reachesequilibrium very fast at the temperatures conventionally utilized in agasifier. This balances the concentrations of carbon monoxide, steam,carbon dioxide and hydrogen, as per the equation:CO+H₂O

CO₂+H₂.  (6)

Essentially, a limited amount of oxygen or air is introduced into thegasifier to allow some of the organic material to be ‘burned’ to producecarbon monoxide and heat energy, which drives a second reaction thatconverts further organic material to hydrogen and carbon dioxide.

Gasification of carbonaceous materials tends to produce undesirably highamounts of carbon dioxide, for example greater than 50 mole percent CO₂.

Therefore, a carbonaceous feedstock may be used as a source forproducing synthesis gas. The produced synthesis gas may have a desiredmole ratio of hydrogen to carbon monoxide and/or comprises a desiredamount of carbon dioxide. In some embodiments, the system and method maybe adjusted depending on the carbonaceous feedstock and/or downstreamprocesses (e.g., FT using a specific FT catalyst) to alter the moleratio of the product synthesis gas as desired for a given application.

A method of producing synthesis gas from carbonaceous material isdescribed. The method comprises: (a) providing a slurry comprisingcarbonaceous material and slurry liquid; (b) subjecting the slurry tohigh shear under gasification conditions whereby a high shear-treatedstream comprising synthesis gas is produced; and (c) separating aproduct comprising synthesis gas from the high shear-treated stream. Inembodiments, (c) further comprises separating slurry liquid from thehigh shear treated stream. In embodiments, (b) subjecting the slurry tohigh shear to produce a high shear-treated stream comprising synthesisgas further comprises contacting the slurry with at least one gas orvapor selected from steam, hydrogen, air, oxygen, and associated gas. Inembodiments, the method further comprises recycling separated unreactedcarbonaceous material, separated slurry liquid or both from (c) to (a).In embodiments, (b) subjecting the slurry to high shear to produce ahigh shear-treated stream comprising synthesis gas comprises subjectingthe slurry to a shear rate of at least 20,000 s⁻¹. In embodiments, thecarbonaceous material comprises coke, coal, peat or a combinationthereof. In embodiments, the carbonaceous material comprises coal, peator a combination thereof. The coal can be selected from bituminous,anthracite, and lignite. In embodiments, (a) providing a slurry furthercomprises comminuting the carbonaceous material to an average powdersize of less than about 75 μm. In embodiments, the slurry liquid isaqueous. In embodiments, the slurry liquid is non-aqueous.

In embodiments, the method further comprises (c) utilizing at least aportion of the produced synthesis gas to produce a different product. Inembodiments, (c) utilizing at least a portion of the synthesis gas toproduce a different product comprises separating the at least a portionof the synthesis gas from the high shear-treated stream. In embodiments,liquid hydrocarbons are produced during (b) and at least a portion ofthe liquid hydrocarbons produced in (b) are used in (c). In embodiments,(c) utilizing at least a portion of the synthesis gas to produce aliquid product comprises forming a dispersion of synthesis gas in aliquid phase. In embodiments, (c) utilizing at least a portion of thesynthesis gas to produce a different product comprises catalyticallyreacting the at least a portion of the synthesis gas to produceFischer-Tropsch hydrocarbons. In embodiments, the liquid productcomprises liquid hydrocarbons and alcohols. In embodiments, the liquidproduct comprises primarily liquid hydrocarbons, primarily alcohols, orsubstantially equivalent amounts of alcohols and liquid hydrocarbons. Inembodiments, the liquid phase comprises one or more liquid hydrocarbonproduced by Fischer-Tropsch, one or more alcohol, or a combinationthereof. In embodiments, the dispersion comprises synthesis gas bubbleshaving an average particle diameter of less than or equal to about 5, 4,3, 2 or 1 μm. In embodiments, the synthesis gas bubbles have an averagediameter of less than or equal to about 100 nm.

In embodiments of the method, forming a dispersion comprises subjectingthe synthesis gas and liquid carrier to a shear rate of at least about20,000 s⁻¹ in a high shear device comprising at least one rotor and atleast one stator, wherein the shear rate is defined as the tip speeddivided by the shear gap, and wherein the tip speed is defined as πDn,where D is the diameter of the at least one rotor and n is the frequencyof revolution. Subjecting the synthesis gas and liquid carrier to ashear rate of at least 20,000 s⁻¹ may produce a local pressure of atleast about 1034.2 MPa (150,000 psi) at a tip of the at least one rotor.In embodiments, forming a dispersion comprises introducing the synthesisgas and liquid carrier into a high shear device comprising at least onerotor and at least one stator and providing a tip speed of at leastabout 23 m/sec, wherein the tip speed is defined as πDn, where D is thediameter of the at least one rotor and n is the frequency of revolution.The method may further comprise introducing the dispersion into areactor comprising a fixed bed of catalyst or a fluidized bed ofcatalyst. The method may further comprise separating unreacted synthesisgas from liquid product. The method may further comprise recycling theunreacted synthesis gas to produce additional dispersion. Inembodiments, the slurry comprises powdered coal and coalbed methane.

Also disclosed is a method of producing liquid product comprisingalcohol from synthesis gas, the method comprising: introducing synthesisgas and liquid carrier into a high shear device comprising at least onerotor and at least one complementarily-shaped stator; and subjecting thecontents of the high shear device to a shear rate of at least 10,000s⁻¹, wherein the shear rate is defined as the tip speed divided by theshear gap, wherein the tip speed is defined as πDn, where D is thediameter of the at least one rotor and n is the frequency of revolution.In embodiments, the synthesis gas is obtained via the high shear methodof producing synthesis gas from carbonaceous materials described above.In embodiments, (a) the synthesis gas further comprises carbon dioxide;(b) carbon dioxide, H₂O, or both is introduced into the high sheardevice with the synthesis gas and liquid carrier; or both (a) and (b).The liquid product may comprise both liquid hydrocarbons and alcohols.In embodiments, the liquid product comprises liquid hydrocarbons,alcohols and water. In embodiments, the liquid product comprises lessthan 10% water. In embodiments, the liquid product comprises more liquidhydrocarbons than alcohols or substantially equal amounts of liquidhydrocarbons and alcohols.

The method may further comprise separating the liquid hydrocarbons fromthe alcohols. The method may further comprise contacting the synthesisgas and liquid carrier with a catalyst. The catalyst may be aFischer-Tropsch catalyst. In embodiments, the catalyst promotes theproduction of alcohols. in embodiments, more than 28 moles of liquidproduced are produced from 100 moles of gas introduced into the highshear device.

Also disclosed is a system for producing synthesis gas from carbonaceousmaterial, the system comprising: apparatus for providing a slurrycomprising carbonaceous material and slurry liquid; at least one highshear device comprising at least one rotor and at least onecomplementarily-shaped stator and configured to subject the slurry tohigh shear and produce a high shear-treated stream comprising synthesisgas, wherein the at least one rotor is configured to provide a tip speedof at least about 23 m/sec, wherein the tip speed is defined as πDn,where D is the diameter of the at least one rotor and n is the frequencyof revolution; and a pump configured for delivering the slurry to the atleast one high shear device. In embodiments, the system furthercomprises a vessel coupled to the at least one high shear device, thevessel configured for receiving a high shear-treated stream from the atleast one high shear device. The at least one rotor may be rotatable ata tip speed of at least 40 m/sec. The at least one rotor may beseparated from the at least one stator by a shear gap in the range offrom in the range of from about 0.02 mm to about 5 mm, wherein the sheargap is the minimum distance between the at least one rotor and the atleast one stator. In embodiments, the shear rate provided by rotation ofthe at least one rotor during operation is at least 20,000 s⁻¹, whereinthe shear rate is defined as the tip speed divided by the shear gap. Inembodiments, the at least one high shear device comprises two or morerotors and two or more stators.

The system may further comprise a line for introducing a dispersible gasor vapor into the slurry upstream of the at least one high shear deviceor into the at least one high shear device. The dispersible gas or vaporcan be selected from air, oxygen, hydrogen, associated gas and steam. Inembodiments, the at least one high shear device is configured forproducing a dispersion comprising bubbles of synthesis gas, bubbles ofdispersible gas or vapor, particles of carbonaceous material, or acombination thereof in a liquid phase comprising slurry liquid, whereinthe dispersion has a mean bubble diameter, a mean particle size, orboth, of less than about 5, 4, 3, 2, 1, 0.5, 0.4, 0.3, 0.2, or 0.1 μm.

In embodiments, the system comprises more than one high shear device. Inembodiments, the at least one high shear device comprises at least twogenerators, wherein each generator comprises a rotor and acomplementarily-shaped stator. The shear rate provided by one generatormay be greater than the shear rate provided by another generator.

The system may further comprise apparatus for the production of liquidhydrocarbons, alcohols or a combination thereof wherein the apparatusfor producing liquid hydrocarbons, alcohols or a combination thereof isfluidly connected with an outlet of the at least one high shear device.In embodiments, the apparatus for the production of liquid hydrocarbons,alcohols or a combination thereof comprises at least one high sheardevice. The at least one high shear device of the apparatus for theproduction of liquid hydrocarbons, alcohols or a combination thereof maycomprise at least one rotor and at least one complementarily-shapedstator. In embodiments, the at least one rotor of the high shear devicefor the production of liquid hydrocarbons, alcohols or a combinationthereof is separated from the at least one stator by a shear gap in therange of from about 0.02 mm to about 5 mm, wherein the shear gap is theminimum distance between the at least one rotor and the at least onestator.

Also disclosed is a system for the production of liquid productcomprising hydrocarbons and alcohols from synthesis gas, the systemcomprising: at least one high shear device comprising at least one rotorand at least one complementarily-shaped stator and configured to subjectsynthesis gas and liquid carrier to high shear and produce a highshear-treated stream comprising liquid product, wherein the at least onerotor is configured to provide a tip speed of at least about 23 m/sec,wherein the tip speed is defined as πDn, where D is the diameter of theat least one rotor and n is the frequency of revolution; and a pumpconfigured for delivering the liquid carrier to the at least one highshear device via a high shear device inlet line. In embodiments, the atleast one high shear device is configured to produce a dispersioncomprising bubbles of synthesis gas dispersed in the liquid carrier. Thebubbles may have an average bubble diameter of less than 5, 4, 3, 2, or1 μm. In embodiments, the bubbles have an average bubble diameter in thesubmicron range. The system may further comprise a catalyst. The systemcan be configured to produce primarily hydrocarbons, primarily alcohols,or substantially equivalent amounts of liquid hydrocarbons and alcohols.

The system may further comprise a vessel having an inlet fluidlyattached to an outlet of the at least one high shear device. Inembodiments, the system further comprises a separation device operableto separate alcohols from liquid hydrocarbons, wherein an inlet of theseparation device is directly or indirectly connected with an outlet ofthe at least one high shear device. In embodiments, the system furthercomprises a line connected to the high shear inlet line for theintroduction of synthesis gas into the at least one high shear device.In embodiments, (a) the synthesis gas comprises carbon dioxide inaddition to carbon monoxide and hydrogen, (b) the system furthercomprises a line connected to the high shear inlet line for theintroduction of carbon dioxide into the at least one high shear device;or both (a) and (b).

Overview.

Herein disclosed are a system and process for producing synthesis gas.The system comprises an external high shear mechanical device to providerapid contact and mixing of reactants in a controlled environment in thereactor/mixer device. A reactor assembly that comprises an external highshear device (HSD) or mixer as described herein may decrease masstransfer limitations and thereby allow the reaction, which may becatalytic, to more closely approach kinetic limitations. Enhanced mixingmay also homogenize the temperature within the reaction zone(s).Enhancing contact via the use of high shear may permit increasedthroughput and/or the use of a decreased amount of catalyst (e.g. FTcatalyst in certain embodiments) relative to conventional processesand/or may enable reactions to occur that would otherwise not beexpected to occur.

High Shear System for Production of Synthesis Gas.

A high shear system 100 for production of synthesis gas will now bedescribed with reference to FIG. 5, which is a process flow diagram of ahigh shear system 100 according to an embodiment of this disclosure. Thebasic components of a representative system include external high sheardevice (HSD) 40 and pump 5. Each of these components is furtherdescribed in more detail below. Line 21 is connected to pump 5 forintroducing feed comprising carbonaceous materials into pump 5. Line 13connects pump 5 to HSD 40, and line 19 carries a high shear-treatedstream out of HSD 40. Synthesis gas production system 100 may furthercomprise a vessel 10. Vessel 10 may be fluidly connected to HSD 40 viahigh shear-treated product flow line 19. Vessel 10 may comprise one ormore outlet lines. For example, in the embodiments of FIG. 5, vessel 10comprises first vessel-10 outlet 16, second vessel-10 outlet 17, andthird vessel-10 outlet 20.

Additional components or process steps can be incorporated between HSD40 and vessel 10 or ahead of pump 5 or HSD 40, if desired, as willbecome apparent upon reading the description of the high shear processhereinbelow. For example, line 20 can be connected to line 21 or line 13from flow line 19 or reactor 10, such that material (e.g. slurry liquidand/or unreacted carbonaceous material) in flow line 19 or from vessel10 may be recycled to HSD 40. Product may be removed from system 100 viaflow line 19. Flow line 19 is any line into which the high shear-treatedstream from HSD 40 (comprising at least liquids and gases and anyunreacted solids from HSD 40) flow.

System 100 may further comprise slurry production apparatus 15 for theproduction of a slurry comprising carbonaceous material, as describedfurther hereinbelow. In embodiments, first dispersible gas line 22 isconfigured to introduce dispersible gas (or vapor, e.g. hydrogen,oxygen, air, associated gas, steam) into HSD 40. Line 22 may introducedispersible gas into HSD 40 directly or may introduce dispersible gasinto line 13.

The synthesis gas production system may further comprise synthesis gasutilization apparatus 30. For example, in the embodiment of FIG. 5,synthesis gas utilization apparatus 30 comprises a second high sheardevice 40 a and a second pump 5 a. Line 21 a is connected to pump 5 afor introducing liquid carrier into pump 5 a. Line 13 a connects pump 5a to HSD 40 a, and line 19 a carries a dispersion out of HSD 40 a.Additional components or process steps can be incorporated after HSD 40a, or ahead of pump 5 a or HSD 40 a, if desired, as will become apparentupon reading the description of the high shear process hereinbelow.Dispersible gas line 22 a fluidly connects first outlet line 16 ofvessel 10 with second HSD 40 a, whereby a portion of the synthesis gasproduced in HSD 40 may be used as dispersible gas in HSD 40 a. Synthesisgas utilization apparatus 30 may further comprise second vessel 10 a.Second vessel 10 a may be connected to HSD 40 a via dispersion outletline 19 a. Second vessel 10 a may comprise one or more outlets, forexample first vessel 10 a outlet line 16 a and second vessel 10 a outletline 17 a.

High Shear Device.

External high shear device (HSD) 40 (and second HSD 40 a, when present),also sometimes referred to as a high shear mixer, is configured forreceiving an inlet stream, via line 13 (13 a). Line 22 (22 a) may beconfigured to introduce dispersible gas (or vapor) into HSD 40 (HSD 40a). Alternatively, HSD 40 may be configured for receiving dispersiblegas and carbonaceous slurry (or dispersible gas and liquid carrier inthe case of HSD 40 a) via separate inlet lines. Although only one HSD isshown for producing synthesis gas in the embodiment of FIG. 5 (i.e.,prior to synthesis gas utilization apparatus 30), it should beunderstood that some embodiments of the system can comprise two or moreHSDs upstream of synthesis gas utilization apparatus 30. The two or moreHSDs can be arranged in either series or parallel flow.

In embodiments, both the rotor and stator comprise a plurality ofcircumferentially-spaced rings having complementarily-shaped tips. Aring may comprise a solitary surface or tip encircling the rotor or thestator. In embodiments, both the rotor and stator comprise more than 2circumferentially-spaced rings, more than 3 rings, or more than 4 rings.For example, in embodiments, each of three generators comprises a rotorand stator each having 3 complementary rings, whereby the materialprocessed passes through 9 shear gaps or stages upon traversing HSD40/40 a. Alternatively, each of three generators may comprise fourrings, whereby the processed material passes through 12 shear gaps orstages upon passing through HSD 40/40 a. In some embodiments, thestator(s) are adjustable to obtain the desired shear gap between therotor and the stator of each generator (rotor/stator set). Eachgenerator may be driven by any suitable drive system configured forproviding the desired rotation.

In some embodiments, HSD 40/40 a comprises a single stage dispersingchamber (i.e., a single rotor/stator combination; a single high sheargenerator). In some embodiments, HSD 40/40 a is a multiple stage inlinedisperser and comprises a plurality of generators. In certainembodiments, HSD 40/40 a comprises at least two generators. In otherembodiments, HSD 40/40 a comprises at least 3 generators. In someembodiments, HSD 40/40 a is a multistage mixer whereby the shear rate(which varies proportionately with tip speed and inversely withrotor/stator gap width) varies with longitudinal position along the flowpathway, as further described hereinbelow.

According to this disclosure, at least one surface within HSD 40/40 amay be made of, impregnated with, or coated with a catalyst suitable forcatalyzing a desired reaction, as described in U.S. patent applicationSer. No. 12/476,415, which is hereby incorporated herein by referencefor all purposes not contrary to this disclosure. For example, inembodiments, all or a portion of at least one rotor, at least onestator, or at least one rotor/stator set (i.e., at least one generator)is made of, coated with, or impregnated with a suitable catalyst. Insome applications, it may be desirable to utilize two or more differentcatalysts. In such instances, a generator may comprise a rotor made of,impregnated with, or coated with a first catalyst material, and thecorresponding stator of the generator may be made of, coated with, orimpregnated by a second catalyst material. Alternatively one or morerings of the rotor may be made from, coated with, or impregnated with afirst catalyst, and one or more rings of the rotor may be made from,coated with, or impregnated by a second catalyst. Alternatively one ormore rings of the stator may be made from, coated with, or impregnatedwith a first catalyst, and one or more rings of the stator may be madefrom, coated with, or impregnated by a second catalyst. All or a portionof a contact surface of a stator, rotor, or both can be made from orcoated with catalytic material.

A contact surface of HSD 40/40 a can be made from a porous sinteredcatalyst material, such as platinum. In embodiments, a contact surfaceis coated with a porous sintered catalytic material. In applications, acontact surface of HSD 40/40 a is coated with or made from a sinteredmaterial and subsequently impregnated with a desired catalyst. Thesintered material can be a ceramic or can be made from metal powder,such as, for example, stainless steel or pseudoboehmite. The pores ofthe sintered material may be in the micron or the submicron range. Thepore size can be selected such that the desired flow and catalyticeffect are obtained. Smaller pore size may permit improved contactbetween fluid comprising reactants and catalyst. By altering the poresize of the porous material (ceramic or sintered metal), the availablesurface area of the catalyst can be adjusted to a desired value. Thesintered material may comprise, for example, from about 70% by volume toabout 99% by volume of the sintered material or from about 80% by volumeto about 90% by volume of the sintered material, with the balance of thevolume occupied by the pores.

In embodiments, the rings defined by the tips of the rotor/statorcontain no openings (i.e. teeth or grooves) such that substantially allof the reactants are forced through the pores of the sintered material,rather than being able to bypass the catalyst by passing through anyopenings or grooves which are generally present in conventionaldispersers. In this manner, for example, a reactant will be forcedthrough the sintered material, thus forcing contact with the catalyst.

In embodiments, the sintered material of which the contact surface ismade comprises stainless steel or bronze. The sintered material(sintered metal or ceramic) may be passivated. A catalyst may then beapplied thereto. The catalyst may be applied by any means known in theart. The contact surface may then be calcined to yield the metal oxide(e.g. stainless steel). The first metal oxide (e.g., the stainless steeloxide) may be coated with a second metal and calcined again. Forexample, stainless steel oxide may be coated with aluminum and calcinedto produce aluminum oxide. Subsequent treatment may provide anothermaterial. For example, the aluminum oxide may be coated with silicon andcalcined to provide silica. Several calcining/coating steps may beutilized to provide the desired contact surface and catalyst(s). In thismanner, the sintered material which either makes up the contact surfaceor coats the contact surface may be impregnated with a variety ofcatalysts. Another coating technique, for example, is metal vapordeposition or chemical vapor deposition, such as typically used forcoating silicon wafers with metal.

In embodiments, a sintered metal contact surface (e.g., of the rotor orthe stator) is treated with a material. For example, tetra ethyl orthosilicate (TEOS). Following vacuum evaporation, TEOS may remain insurface pores. Calcination may be used to convert the TEOS to silica.This impregnation may be repeated for all desired metal catalysts. Uponformation, coating, or impregnation, the catalyst(s) may be activatedaccording to manufacturer's protocol. For example, catalysts may beactivated by contacting with an activation gas, such as hydrogen. Thebase material may be silicon or aluminum which, upon calcination, isconverted to alumina or silica respectively. Suitable catalysts,including without limitation, rhenium, palladium, rhodium, etc. cansubsequently be impregnated into the pores. The catalyst may be acatalyst effective for catalyzing FT reactions, as discussed furtherhereinbelow.

In some embodiments, the minimum clearance (shear gap width) between thestator and the rotor is in the range of from about 0.025 mm (0.001 inch)to about 3 mm (0.125 inch). In some embodiments, the minimum clearance(shear gap width) between the stator and the rotor is in the range offrom about 1 μm (0.00004 inch) to about 3 mm (0.012 inch). In someembodiments, the minimum clearance (shear gap width) between the statorand the rotor is less than about 10 μm (0.0004 inch), less than about 50μm (0.002 inch), less than about 100 μm (0.004 inch), less than about200 μm (0.008 inch), less than about 400 μm (0.016 inch). In certainembodiments, the minimum clearance (shear gap width) between the statorand rotor is about 1.5 mm (0.06 inch). In certain embodiments, theminimum clearance (shear gap width) between the stator and rotor isabout 0.2 mm (0.008 inch). In certain configurations, the minimumclearance (shear gap) between the rotor and stator is at least 1.7 mm(0.07 inch). The shear rate produced by the HSD may vary withlongitudinal position along the flow pathway. In some embodiments, therotor is set to rotate at a speed commensurate with the diameter of therotor and the desired tip speed. In some embodiments, the HSD has afixed clearance (shear gap width) between the stator and rotor.Alternatively, the HSD has adjustable clearance (shear gap width). Theshear gap may be in the range of from about 5 micrometers (0.0002 inch)and about 4 mm (0.016 inch).

The frequency of revolution of the HSD rotor may be greater than 250rpm, greater than 500 rpm, greater than 1000 rpm, greater than 5000 rpm,greater than 7500 rpm, greater than 10,000 rpm, greater than 13,000 rpm,or greater than 15,000 rpm. The rotational frequency, flow rate, andtemperature may be adjusted to get a desired product profile. Ifchanneling should occur, and some reactants pass through unreacted, therotational frequency may be increased to minimize undesirablechanneling. Alternatively or additionally, unreacted reactants may beintroduced into a second or subsequent HSD 40, or a portion of theunreacted reactants may be separated from the products and recycled toHSD 40.

HSD 40/40 a may provide a tip speed in excess of 22.9 m/s (4500 ft/min)and may exceed 40 m/s (7900 ft/min), 50 m/s (9800 ft/min), 100 m/s(19,600 ft/min), 150 m/s (29,500 ft/min), 200 m/s (39,300 ft/min), oreven 225 m/s (44,300 ft/min) or greater in certain applications. For thepurpose of this disclosure, the term ‘high shear’ refers to mechanicalrotor stator devices (e.g., colloid mills or rotor-stator dispersers)that are capable of tip speeds in excess of 5.1 m/s (1000 ft/min) orthose values provided above and require an external mechanically drivenpower device to drive energy into the stream of products to be reacted.By contacting the reactants with the rotating members, which can be madefrom, coated with, or impregnated with stationary catalyst, significantenergy is transferred to the reaction. Especially in instances where thereactants are gaseous, the energy consumption of the HSD 40/40 a will bevery low. The temperature may be adjusted to control the product profileand to extend catalyst life.

An approximation of energy input into the fluid (kW/L/min) can beestimated by measuring the motor energy (kW) and fluid output (L/min).As mentioned above, tip speed is the velocity (ft/min or m/s) associatedwith the end of the one or more revolving elements that is creating themechanical force applied to the fluid. In embodiments, the energyexpenditure is at least about 1000 W/m³, 5000 W/m³, 7500 W/m³, 1 kW/m³,500 kW/m³, 1000 kW/m³, 5000 kW/m³, 7500 kW/m³, or greater. Inembodiments, the energy expenditure of HSD 40/40 a is greater than 1000watts per cubic meter of fluid therein. In embodiments, the energyexpenditure of HSD 40/40 a is in the range of from about 3000 W/m³ toabout 7500 kW/m³. In embodiments, the energy expenditure of HSD 40 is inthe range of from about 3000 W/m³ to about 7500 W/m³. The actual energyinput needed is a function of what reactions are occurring within theHSD, for example, endothermic and/or exothermic reaction(s), as well asthe mechanical energy required for dispersing and mixing feedstockmaterials. In some applications, the presence of exothermic reaction(s)occurring within the HSD mitigates some or substantially all of thereaction energy needed from the motor input. When dispersing a gas in aliquid, the energy requirements are significantly less.

The shear rate is the tip speed divided by the shear gap width (minimalclearance between the rotor and stator). The shear rate generated in HSD40/40 a may be in the greater than 20,000 s⁻¹. In some embodiments theshear rate is at least 30,000 s⁻¹ or at least 40,000 s⁻¹. In someembodiments the shear rate is greater than 30,000 s⁻¹. In someembodiments the shear rate is at least 100,000 s⁻¹. In some embodimentsthe shear rate is at least 500,000 s⁻¹. In some embodiments the shearrate is at least 1,000,000 s⁻¹. In some embodiments the shear rate is atleast 1,600,000 s⁻¹. In some embodiments the shear rate is at least3,000,000 s⁻¹. In some embodiments the shear rate is at least 5,000,000s⁻¹. In some embodiments the shear rate is at least 7,000,000 s⁻¹. Insome embodiments the shear rate is at least 9,000,000 s⁻¹. Inembodiments where the rotor has a larger diameter, the shear rate mayexceed about 9,000,000 s⁻¹. In embodiments, the shear rate generated byHSD 40/40 a is in the range of from 20,000 s⁻¹ to 10,000,000 s⁻¹.

In embodiments, a scaled-up version of the DISPAX® reactor is utilized.For example, in embodiments HSD 40/40 a comprises a SUPER DISPAXREACTOR® DRS 2000. The HSD unit may be a DR 2000/50 unit, having a flowcapacity of 125,000 liters per hour, or a DRS 2000/50 having a flowcapacity of 40,000 liters/hour. Because residence time is increased inthe DRS unit, the fluid therein is subjected to more shear.

First generator 220 comprises rotor 222 and stator 227. Second generator230 comprises rotor 223, and stator 228. Third generator 240 comprisesrotor 224 and stator 229. For each generator the rotor is rotatablydriven by input 250 and rotates about axis 260 as indicated by arrow265. The direction of rotation may be opposite that shown by arrow 265(e.g., clockwise or counterclockwise about axis of rotation 260).Stators 227, 228, and 229 may be fixably coupled to the wall 255 of HSD200. As mentioned hereinabove, each rotor and stator may comprise ringsof complementarily-shaped tips, leading to several shear gaps withineach generator.

As discussed above, a contact surface of the HSD 40/40 a/200 may be madefrom, coated with, or impregnated by a suitable catalyst which catalyzesthe desired reaction. In embodiments, a contact surface of one ring ofeach rotor or stator is made from, coated with, or impregnated with adifferent catalyst than the contact surface of another ring of the rotoror stator. Alternatively or additionally, a contact surface of one ringof the stator may be made from coated with or impregnated by a differentcatalyst than the complementary ring on the rotor. The contact surfacemay be at least a portion of the rotor, at least a portion of thestator, or both. The contact surface may comprise, for example, at leasta portion of the outer surface of a rotor, at least a portion of theinner surface of a stator, or at least a portion of both.

HSD 200 may be configured so that the shear rate remains the same orincreases or decreases stepwise longitudinally along the direction ofthe flow 260.

Generators 220, 230, and 240 may comprise a coarse, medium, fine, andsuper-fine characterization, having different numbers of complementaryrings or stages on the rotors and complementary stators. Althoughgenerally less desirable, rotors 222, 223, and 224 and stators 227, 228,and 229 may be toothed designs. Each generator may comprise two or moresets of complementary rotor-stator rings. In embodiments, rotors 222,223, and 224 comprise more than 3 sets of complementary rotor/statorrings. In embodiments, the rotor and the stator comprise no teeth, thusforcing the reactants to flow through the pores of a sintered material.

HSD 40/40 a may be a large or small scale device. In embodiments, HSD40/40 a is used to process from less than 10 tons per hour to 50 tonsper hour. In embodiments, HSD 40/40 a processes 10 tons/h, 20 tons/h, 30ton/hr, 40 tons/h, 50 tons/h, or more than 50 tons/h. Large scale unitsmay produce 1000 gal/h (24 barrels/h). The inner diameter of the rotormay be any size suitable for a desired application. In embodiments, theinner diameter of the rotor is from about 12 cm (4 inch) to about 40 cm(15 inch). In embodiments, the diameter of the rotor is about 6 cm (2.4inch). In embodiments, the outer diameter of the stator is about 15 cm(5.9 inch). In embodiments, the diameter of the stator is about 6.4 cm(2.5 inch). In some embodiments the rotors are 60 cm (2.4 inch) and thestators are 6.4 cm (2.5 inch) in diameter, providing a clearance ofabout 4 mm. In certain embodiments, each of three stages is operatedwith a super-fine generator comprising a number of sets of complementaryrotor/stator rings.

HSD 200 is configured for receiving at inlet 205 a fluid mixture fromline 13. The mixture comprises reactants. In embodiments, the reactantscomprise carbon and oxygen and/or steam. In embodiments, the reactantscomprise hydrogen and carbon monoxide. In embodiments, at least onereactant is gaseous. In embodiments, at least one reactant is solid.Feed stream entering inlet 205 is pumped serially through generators220, 230, and then 240, such that product is formed. Product exits HSD200 via outlet 210 (and line 19 of FIG. 5). The rotors 222, 223, 224 ofeach generator rotate at high speed relative to the fixed stators 227,228, 229, providing a high shear rate. The rotation of the rotors pumpsfluid, such as the feed stream entering inlet 205, outwardly through theshear gaps (and, if present, through the spaces between the rotor teethand the spaces between the stator teeth), creating a localized highshear condition. High shear forces exerted on fluid in shear gaps 225,235, and 245 (and, when present, in the gaps between the rotor teeth andthe stator teeth) through which fluid flows process the fluid and createproduct. The product may comprise a dispersion of unreacted or productgas and/or unreacted carbonaceous material in a continuous phase ofliquid (e.g., liquid hydrocarbon product and/or slurry liquid and/orcarrier liquid). The high shear-treated stream 19 may comprise unreactedsolid carbonaceous material. Product exits HSD 200 via high shear outlet210 (lines 19/19 a of FIG. 5).

As mentioned above, in certain instances, HSD 200 comprises a DISPAXREACTOR® of IKA® Works, Inc. Wilmington, N.C. and APV North America,Inc. Wilmington, Mass. Several models are available having variousinlet/outlet connections, horsepower, tip speeds, output rpm, and flowrate. Selection of the HSD will depend on throughput selection anddesired particle, droplet or bubble size in dispersion in line 19/19 a(FIG. 5) exiting outlet 210 of HSD 200. IKA® model DR 2000/4, forexample, comprises a belt drive, 4M generator, PTFE sealing ring, inletflange 25.4 mm (1 inch) sanitary clamp, outlet flange 19 mm (¾ inch)sanitary clamp, 2 HP power, output speed of 7900 rpm, flow capacity(water) approximately 300-700 L/h (depending on generator), a tip speedof from 9.4-41 m/s (1850 ft/min to 8070 ft/min). Scale up may beperformed by using a plurality of HSDs, or by utilizing larger HSDs.Scale-up using larger models is readily performed, and results fromlarger HSD units may provide improved efficiency in some instancesrelative to the efficiency of lab-scale devices. The large scale unitmay be a DISPAX® 2000/unit. For example, the DRS 2000/5 unit has aninlet size of 51 mm (2 inches) and an outlet of 38 mm (1.5 inches).

In embodiments HSD 40/40 a or portions thereof are manufactured fromrefractory/corrosion resistant materials. For example, sintered metals,INCONEL® alloys, HASTELLOY® materials may be used. For example, ash fromthe coal may be very abrasive, so the rotors, stators, and/or othercomponents of HSD 40 may be manufactured of abrasion resistant materials(e.g. sintered metal) in applications wherein carbonaceous materialcomprises coal. The HSD utilized for significant gas production will bedesigned as known in the art to withstand any increase in pressureanticipated therein during operation.

Vessel.

Vessel or reactor 10 (and 10 a) can be any type of vessel in which amultiphase reaction can be propagated to carry out the above-describedconversion reaction(s) or can be a separation vessel configured toseparate gas, liquid, and/or solids introduced thereto via highshear-treated line 19/19 a. In embodiments, vessel 10 is a separationvessel. Vessel 10/10 a may be a continuous or semi-continuous stirredtank reactor, or one or more batch reactors may be employed in series orin parallel. In some applications vessel 10/10 a may be a tower reactor,and in others a tubular reactor or multi-tubular reactor. Vessel 10/10 amay be a fluidized bed reactor a fixed bed reactor or a slurry bedreactor. In embodiments, vessel 10 a is a fixed bed reactor, a slurrybed reactor, or a fluidized bed reactor, as discussed furtherhereinbelow. A catalyst inlet line may be connected to vessel 10/10 afor receiving a catalyst solution or slurry during operation of thesystem. In embodiments where a significant reaction occurs in HSD 40,vessel 10 may comprise one or more fractionators suitable for separatingcomponents. In embodiments, the components separated in vessel 10 areselected from synthesis gas, unreacted carbonaceous material, liquidhydrocarbon product, slurry liquid, or any combination thereof. In theembodiment of FIG. 5, vessel 10 comprises first vessel-10 outlet line16, second vessel-10 outlet line 17 and third vessel-10 outlet line 20.In the embodiment of FIG. 5, vessel 10 a comprises first vessel-10 aoutlet line 16 a and second vessel-10 a outlet line 17 a.

Vessel 10/10 a may include one or more of the following components:stirring system, heating and/or cooling capabilities, pressuremeasurement instrumentation, temperature measurement instrumentation,one or more injection points, and level regulator, as are known in theart of reaction vessel design. For example, a stirring system mayinclude a motor driven mixer. A heating and/or cooling apparatus maycomprise, for example, a heat exchanger. Alternatively, as much of thedesired reaction may occur within the HSD in some embodiments, vessel10/10 a may serve primarily as a storage vessel in some cases. Althoughgenerally less desired, in some applications vessel 10/10 a may beomitted, particularly if multiple high shears/reactors are employed inseries, as further described below.

Slurry Production Apparatus.

System 100 may further comprise slurry production apparatus 15. Slurryproduction apparatus is any apparatus suitable for providing a slurry ofcarbonaceous material in suitable slurry liquid or diluent. The diluent(slurry liquid) may be aqueous, non-aqueous. The slurry liquid maycomprise one or more component selected from oils, water, and alcohols.The carbonaceous material may be coal, coke, or a combination thereof.In embodiments, the carbonaceous material is selected from lignite,anthracite, bituminous, and sub-bituminous coals.

The term “coal” is used herein to describe a variety of fossilized plantmaterials. No two coals are exactly alike. Heating value, ash meltingtemperature, sulfur and other impurities, mechanical strength, and manyother chemical and physical properties must be considered when matchingspecific coals to a particular application.

Coal is classified into four general categories, or ‘ranks.’ They rangefrom lignite through sub-bituminous and bituminous to anthracite,reflecting the progressive response of individual deposits of coal toincreasing heat and pressure. The carbon content of coal supplies mostof its heating value, but other factors also influence the amount ofenergy it contains per unit of weight. The amount of energy in coal isexpressed in British thermal units (BTU) per pound. A BTU is the amountof heat required to raise the temperature of one pound of water onedegree Fahrenheit.

In embodiments, the carbonaceous material comprises lignite. Ligniteranks the lowest and is the youngest of the coals. Lignite is ageologically young coal which has the lowest carbon content, 25-35percent, and a heat value ranging between 4,000 and 8,300 BTU/lb. Inembodiments, the carbonaceous material comprises lignite which has acarbon content of around 25-35% and a high inherent moisture content(may be, e.g., as high as 66%). The ash content of lignite may be in therange of from about 6% to 19%, compared with 6% to 12% for bituminouscoal. The heat content of the lignite may range from 10 to 20 MJ/kg (9to 17 million BTU per short ton) on a moist, mineral-matter-free basis.The heat content of the lignite may average about 13 million BTU/ton (15MJ/kg), on the as-received basis (i.e., containing both inherentmoisture and mineral matter).

Lignite has a high content of volatile matter which may make it easierto convert into gas and liquid petroleum products than higher rankingcoals. However, its high moisture content and susceptibility tospontaneous combustion can cause problems in transportation, storage,and handling.

In embodiments, the carbonaceous material comprises anthracite.Anthracite is the highest of the metamorphic rank, having the highestcarbon content. In embodiments, the carbonaceous material comprisesanthracite containing between 86 and 98 percent carbon content. Theanthracite may have a heat value of nearly 15,000 BTU/lb. Inembodiments, the anthracite has a carbon content in the range of between92% and 98%. The term ‘anthracite’ is applied to those varieties of coalwhich do not give off tarry or other hydrocarbon vapors when heatedbelow their point of ignition.

Anthracite differs from ordinary bituminous coal by its greaterhardness, its higher relative density of 1.3-1.4, and luster, which isoften semi-metallic with a mildly brown reflection. It contains a highpercentage of fixed carbon and a low percentage of volatile matter. Itis also free from included soft or fibrous notches and does not soil thefingers when rubbed. Anthracitization is the transformation ofbituminous into anthracite.

The moisture content of fresh-mined anthracite generally is less than 15percent. The heat content of the anthracite used as carbonaceousmaterial may range from 22 to 28 million BTU per short ton (26 to 33MJ/kg) on a moist, mineral-matter-free basis. The heat content of theanthracite coal may average 25 million BTU/ton (29 MJ/kg), on theas-received basis (i.e., containing both inherent moisture and mineralmatter).

In embodiments, the carbonaceous material comprises bituminous and/orsub-bituminous coals, which rank below anthracite and, for the mostpart, contain less energy per unit of weight.

In embodiments, the carbonaceous material comprises bituminous coal.Bituminous coal has a carbon content ranging from 45 to 86 percentcarbon and a heat value of 10,500 to 15,500 BTU/lb. In embodiments, thecarbonaceous material comprises bituminous coal having a carbon contentin the range of from about 60% to about 80%; the rest is balance beingwater, air, hydrogen, and/or sulfur. The heat content of the bituminouscoal used as carbonaceous material may range from 21 million to 30million BTU/ton (24 to 35 MJ/kg) on a moist, mineral-matter-free basis.

In embodiments, the carbonaceous material comprises sub-bituminous coal.Ranking below bituminous is sub-bituminous coal with 35-45 percentcarbon content and a heat value between 8,300 and 13,000 BTU/lb.Although its heat value is lower, this coal generally has a lower sulfurcontent than other types, which may make it attractive for use herein.In embodiments, the sub-bituminous coal has a sulfur content less than1% by weight, making it attractive to reduce SO₂ production.Sub-bituminous coal is a type of coal whose properties range from thoseof lignite to those of bituminous coal and is primarily used as fuel forsteam-electric power generation. In embodiments, the sub-bituminous coalcontains 15-30% inherent moisture by weight. The heat content of thesub-bituminous coal used as carbonaceous material may be in the range offrom 8300 to 11,500 BTU/lb or 19,306 to 26,749 kJ/kg. The relatively lowdensity and high water content renders some types of sub-bituminouscoals susceptible to spontaneous combustion if not packed densely duringstorage in order to exclude free air flow, so handling should beadjusted accordingly, as known in the art.

In embodiments, the carbonaceous material comprises coke. Slurryproduction apparatus 15 may thus comprise coke-producing apparatus.Pyrolysis is the chemical decomposition of a condensed substance byheating. Pyrolysis is a special case of thermolysis, most commonly usedfor organic materials. Pyrolysis is used on a massive scale to turn coalinto coke for metallurgy, especially steelmaking. Coke can also beproduced from the solid residue left from petroleum refining. Thepyrolysis production apparatus may be configured for producing coke fromstarting materials typically contain hydrogen, nitrogen or oxygen atomscombined with carbon into molecules of medium to high molecular weight.The coke may be produced by a coking process comprising heating thematerial in closed vessel(s) to very high temperatures (up to 2000° C.),so that those molecules are broken down into lighter volatilesubstances, which leave the vessel, and a porous but hard residue thatis mostly carbon and inorganic ash. The amount of volatiles varies withthe source material, but is typically 25-30% of it by weight.

The slurry production apparatus 15 may comprisecrushing/grinding/pulverizing devices for comminuting the carbonaceousmaterial to a desired size. The carbonaceous material may be processedto a powder having an average particle size of less than 80 μm, lessthan 60 μm, or less than 40 μm, for example. In embodiments, thecarbonaceous comprises coal and the coal powder has a particle size suchthat 70 to 80% of the powder passes through a 200-mesh sieve (74μ). Inembodiments, the slurry is a coal slurry having a particle sizedistribution (PSD) with 10, 20, 30, 40, 50, 60, 70, 80, or 90% of theparticles smaller than about 80, 70, 60, 50, 40, 30, or 20 microns. Acoal slurry may be prepared by any methods known in the art, forexample, as described in the book Alternative Fuels by Sunggyu Lee; CRCPress, 1996, ISBN 1560323612, 9781560323617. In embodiments the coal canfirst be crushed and classified to a powder by means of devices such as,but not limited to, roller mills and cyclone separators. This processingmay be followed by direct conversion to a slurry via means known in theart, such as via wet milling devices, including, but not limited to,attritor mills and ultrasonic mills. Alternatively various colloid millscan be used to prepare slurries from coal.

The slurry production apparatus 15 may further comprise mixing apparatusfor combining powdered carbonaceous material with slurry liquid. Inembodiments, the slurry liquid is aqueous. In embodiments, the slurryliquid is non-aqueous based. The composition of the slurry may beadjusted depending on the carbonaceous material, the dispersible gas orvapor 22 utilized and the operating conditions within HSD 40 such thatsynthesis gas having a desired composition is produced.

Heat Transfer Devices.

Internal or external heat transfer devices for heating the fluid to betreated are also contemplated in variations of the system. For example,the reactants may be preheated via any method known to one skilled inthe art. Some suitable locations for one or more such heat transferdevices are between pump 5 (5 a) and HSD 40 (40 a), between HSD 40 (40a) and flow line 19 (19 a), and between flow line 19 (19 a) and pump 5(5 a) when fluid in flow line 19 (19 a) is recycled to HSD 40 (40 a).HSD may comprise an inner shaft which may be cooled, for examplewater-cooled, to partially or completely control the temperature withinthe HSD. Some non-limiting examples of such heat transfer devices areshell, tube, plate, and coil heat exchangers, as are known in the art.

Pumps.

Pump 5 (5 a) is configured for either continuous or semi-continuousoperation. The capabilities and configuration of pump 5 are describedherein above. In addition to pump 5/5 a, one or more additional, highpressure pumps may be included in the system illustrated in FIG. 5. Forexample, a booster pump, which may be similar to pump 5/5 a, may beincluded between HSD 40 (40 a) and flow line 19 (19 a) for boosting thepressure into flow line 19 (19 a).

Synthesis Gas Utilization Apparatus.

System 100 may further comprise synthesis gas utilization apparatus 30.Synthesis gas utilization apparatus 30 can be any apparatus known in theart for utilization of synthesis gas for producing value-added product,or may comprise a product sales line. In embodiments, synthesis gasutilization apparatus 30 comprises apparatus for the production ofhydrocarbon liquids (e.g. FT hydrocarbons) and/or alcohols fromsynthesis gas. The synthesis gas utilization apparatus 30 can compriseapparatus for reacting synthesis gas in the presence of FT catalyst toproduce FT product comprising liquid hydrocarbons. In embodiments, thesynthesis gas utilization apparatus comprises a slurry bed reactoroperated with a circulating slurry of FT catalyst, a fixed bed reactorcomprising a fixed bed of FT catalyst, or a fluidized bed comprising afluidized bed of FT catalyst. In embodiments, synthesis gas productionapparatus 30 comprises apparatus for the production of methanol fromsynthesis gas. In embodiments, both liquid hydrocarbons and alcohols areproduced in synthesis gas utilization apparatus 30.

In embodiments, as indicated in FIG. 5, synthesis gas utilizationapparatus 30 comprises a second HSD 40 a and a second pump 5 a. HSD 40 aand pump 5 a are similar or identical respectively to HSD 40 and pump 5described above. Line 21 a is connected to pump 5 a for introducingliquid carrier into pump 5 a. Line 13 a connects pump 5 a to HSD 40 a,and line 19 a carries a dispersion out of HSD 40 a. Synthesis gasutilization apparatus 30 may further comprise a vessel 10 a. Asmentioned hereinabove, vessel 10 a may be an FT reactor. In embodiments,vessel 10 may be a fluidized, slurry, or fixed bed reactor. Vessel 10 amay be fluidly connected to HSD 40 a via dispersion flow line 19 a.Vessel 10 a may comprise one or more outlet lines. For example, in theembodiment of FIG. 5, vessel 10 a comprises first vessel-10 a outletline 16 a, second vessel-10 a outlet line 17 a.

Synthesis gas utilization apparatus 30 may contain or utilize an FTcatalyst. A variety of catalysts can be used to catalyze Fischer-Tropschreactions, but the most common are the transition metals cobalt, iron,and ruthenium. Nickel can also be used, but tends to favor methaneformation. Cobalt seems to be the most active catalyst, although ironalso performs well and can be more suitable for low-hydrogen-contentsynthesis gases such as those derived from coal due to its promotion ofthe water-gas-shift reaction. In addition to the active metal thecatalysts can contain a number of promoters, including potassium andcopper, as well as high-surface-area binders/supports such as silica,alumina, and/or zeolites.

Unlike the other metals used for this process (Co, Ni, Ru) which remainin the metallic state during synthesis, iron catalysts tend to form anumber of chemical phases, including various iron oxides and ironcarbides during the reaction. Control of these phase transformations canbe important in maintaining catalytic activity and preventing breakdownof the catalyst particles.

The Fischer-Tropsch catalysts are notoriously sensitive to the presenceof sulfur-containing compounds among other poisons. The sensitivity ofthe catalyst to sulfur is higher for cobalt-based catalysts than fortheir iron counterparts. In embodiments in which the synthesis gasproduced via the disclosed method comprises a substantial amount ofsulfur, cleanup apparatus may be inserted in system 100 upstream of theFT production apparatus. For example, one or more AGRU (acid gas removalunit) or scrubber may be configured to remove sulfur andsulfur-compounds from the produced synthesis gas prior to FT reaction.Additionally, one or more CO₂ removal units may be positioned upstreamof one or more FT reactors for removing at least a portion of the carbondioxide from the synthesis gas prior to FT reaction. For example, one ormore AGRU (acid gas removal unit) may be configured to remove carbondioxide from the produced synthesis gas prior to FT reaction. Inembodiments, alcohols are desired liquid product along with liquidhydrocarbons, and removal of carbon dioxide is unnecessary andundesired. In such embodiments, no CO₂ removal units are incorporated.

Generally, if the synthesis gas has a high hydrogen to carbon ratio, andthe water-gas-shift is not needed, the FT catalyst may comprise cobalt,due to the higher activity of the cobalt catalyst. Iron catalysts may bepreferred when water gas shift is desirable. While iron catalysts arealso susceptible to sulfur poisoning from coal with high sulfur content,the lower cost of iron makes sacrificial catalyst at the front of areactor bed economical. Also, as mentioned earlier, iron can catalyzethe water-gas-shift to increase the hydrogen to carbon ratio to make thereaction more favorably selective, in some embodiments.

System for Utilization of Synthesis Gas.

Also disclosed is a system for the utilization of synthesis gas toproduce liquid product comprising hydrocarbons and alcohols. Such asystem comprises synthesis gas utilization apparatus 30, but may or maynot include high shear device 40, pump 5, and/or vessel 10 for theproduction of the synthesis gas. That is, the synthesis gas utilizationapparatus 30 may be combined with apparatus for the production ofsynthesis gas other than that described above or may be utilized withsynthesis gas from any source (e.g., purchased synthesis gas, synthesisgas obtained via natural gas splitting, etc).

High Shear Process for Producing Synthesis Gas.

A process for producing synthesis gas from slurry comprisingcarbonaceous material will now be described with respect to FIG. 6 whichis a schematic of a method 300 of producing synthesis gas according toan embodiment of this disclosure. Process 300 comprises providingcarbonaceous slurry 400; subjecting the slurry to high shear to producea high shear-treated stream comprising synthesis gas 500; and utilizingsynthesis gas 600.

Providing Carbonaceous Slurry 400.

Providing a carbonaceous slurry 400 may comprise mixing one or morecarbonaceous material with a suitable liquid or diluent to form a slurrythereof. The liquid may be any liquid known in the art to be suitablefor producing a slurry. The liquid may be aqueous or nonaqueous. Forexample, the liquid of the slurry may be selected from water, oils,alcohols, and combinations thereof. The carbonaceous material may beselected from coal and coke. In embodiments, the coke is produced bypyrolizing coal. In embodiments, coke is produced or obtained fromcoking of residuum in a refinery. In embodiments the carbonaceousmaterial comprises lignite, anthracite, bituminous, or a combinationthereof. Providing carbonaceous slurry may further comprise obtainingcoal and comminuting the coal to provide a powder having an averagepowder size less than a desired size. Providing a slurry may furthercomprise comminuting a carbonaceous material to powdered form. Inembodiments, the carbonaceous material powder has an average particlesize of less than about 40, less than about 500, or less than about 1000microns. The ultimate particle size of the carbonaceous materialremaining in the dispersion will be determined by the shear gap of theHSD and/or the pore size of the sintered metal coated rotor and/orstator of the HSD.

Subjecting Slurry to High Shear to Produce High Shear-Treated StreamComprising Synthesis Gas 500.

Process 300 further comprises subjecting the slurry to high shear toproduce a high shear-treated stream comprising synthesis gas 500.Subjecting the slurry to high shear 500 may comprise subjecting theslurry to a shear rate of at least 20,000 s⁻¹, above 30,000 s⁻¹, orgreater, as further discussed hereinbelow. In embodiments, subjectingthe slurry to high shear 500 comprises introducing the slurry into a HSD40, as indicated in FIG. 5. Subjecting the slurry to high shear maycomprise forming a dispersion comprising bubbles of dispersible gas orsynthesis gas or particles of carbonaceous material dispersed in theslurry liquid. In embodiments, the bubbles and/or particles in thedispersion have an average diameter of less than or about 5, 4, 3, 2, or1 μm. In embodiments, the bubbles and/or particles in the dispersionhave an average particle diameter in the nanometer range, the micronrange, or the submicron range.

Referring now to FIG. 5, subjecting the slurry to high shear 500 maycomprise introducing the slurry from slurry production apparatus 15 intoHSD 40. Pump 5 is used to pump the slurry into HSD 40. If desired, gas(or water vapor) may be introduced into pressurized slurry line 13 ordirectly into HSD 40 via dispersible gas (or vapor) line 22. Thecomposition and utilization of dispersible gas can be selected accordingto the carbonaceous materials to be converted to synthesis gas, theoperating conditions and/or the desired H₂:CO mole ratio in theresulting synthesis gas product. For example, when the slurry comprisescarbonaceous material having high carbon and insufficient hydrogencontent (e.g., anthracite and/or bituminous), hydrogen may be introducedinto HSD 40 via dispersible gas line 22. In embodiments, oxygen may beadded via dispersible gas line 22. In embodiments, associated gas may beadded via dispersible gas line 22. In embodiments, water vapor (steam)is introduced via dispersible gas line. HSD 40 may be a rotor-statordevice as described hereinabove. In other embodiments, the dispersiblegas or vapor is present in the slurry as provided in slurry productionapparatus 15 or is introduced directly into HSD 40.

In embodiments, associated gas is combined with the slurry upstream orwithin the HSD 40. For example, if system 100 is incorporated into acoal mining operation, and associated gas is recovered from a coaldeposit with the coal to be used as carbonaceous material, theassociated gas may be introduced into HSD 40 along with the carbonaceousmaterial. The associated gas may be incorporated into the slurry inslurry production apparatus 15, introduced separately via dispersiblegas line 22, or introduced directly into HSD 40. Addition of associatedgas in this manner may be used to increase the H₂:CO mole ratio in theresulting synthesis gas produced in HSD 40. As mentioned herein withregard to Eq. (3), natural gas has a greater hydrogen content (from x=4to x˜2.5) than coal. The term ‘associated gas is used herein to refer togas found deposited in or above coal, e.g. coalbed methane or coal seamgas. The associated gas comprises methane and may comprise various othergases, as known in the art. Coalbed methane may be ‘sweet gas’comprising little hydrogen sulfide. Coalbed methane may contain verylittle heavier hydrocarbons such as propane or butane, and no naturalgas condensate. The associated gas may contain up to a few percentcarbon dioxide.

An inert gas such as nitrogen may be used to fill reactor 10 and purgeit of any air and/or oxygen prior to operation of system 100. Pump 5 isoperated to pump the slurry through line 21, and to build pressure andfeed HSD 40, providing a controlled flow throughout high shear (HSD) 40and high shear system 100. In some embodiments, pump 5 increases thepressure of the HSD inlet stream in line 13 to greater than 200 kPa (2atm) or greater than about 300 kPa (3 atmospheres). In this way, highshear system 100 may combine high shear with pressure to enhanceproduction of synthesis gas.

In embodiments, dispersible gas is continuously fed into the slurrystream 13 to form the high shear feed stream (e.g. a gas-liquid-solidfeed stream). Within high shear device 40, dispersible gas and/orproduct synthesis gas and/or carbonaceous material may be highlydispersed such that nanobubbles and/or microbubbles of gas and/ornanoparticles and/or microparticles of the carbonaceous material areformed. The temperature and shear within HSD 40 are controlled toproduce synthesis gas having a desired composition. For example, thetemperature and shear to which the HSD contents are subjected may beselected/adjusted to produce synthesis gas comprising hydrogen andcarbon monoxide in a desired ratio. The desired synthesis gas H₂:CO moleratio may be in the range of from about 0.5 to 2, in the range of from0.5 to 1.5, in the range of from about 0.7 to 1.5, in the range of fromabout 0.9 to 1.3. The desired synthesis gas may have a H₂:CO mole ratioof about 1:1.

Within HSD 40, the contents are subjected to high shear. It is alsoenvisaged that a catalyst may additionally be present in the HSD 40 incertain embodiments. Components of the carbonaceous material (e.g.metals in the coal ash) may serve to catalyze production of synthesisgas and/or production of liquid hydrocarbons from the synthesis gas. Inembodiments, additional solid, gaseous or liquid phase catalyst may beintroduced to HSD 40 via inlet line 13, line 21, or line 22. In anexemplary embodiment, the high shear device comprises a commercialdisperser such as IKA® model DR 2000/4, a high shear, three stagedispersing device configured with three rotors in combination withstators, aligned in series, as described above. The disperser is used tosubject the slurry to high shear. The rotor/stator sets may beconfigured as illustrated in FIG. 2, for example. In such an embodiment,the feed enters the high shear device via line 13 and enter a firststage rotor/stator combination having circumferentially spaced firststage shear openings. The coarse dispersion (comprising solidcarbonaceous materials and/or gas, i.e. dispersible gas from line 22 orproduct synthesis gas, dispersed in liquid carrier of slurry) exitingthe first stage enters the second rotor/stator stage, which has secondstage shear openings. The reduced particle-size dispersion emerging fromthe second stage enters the third stage rotor/stator combination havingthird stage shear openings. The rotors and stators of the generators mayhave circumferentially spaced complementarily-shaped rings. A highshear-treated stream exits the high shear device via line 19. In someembodiments, the shear rate increases stepwise longitudinally along thedirection of the flow 260, or going from an inner set of rings of onegenerator to an outer set of rings of the same generator. In otherembodiments, the shear rate decreases stepwise longitudinally along thedirection of the flow, 260, or going from an inner set of rings of onegenerator to an outer set of rings of the same generator (outward fromaxis 200). For example, in some embodiments, the shear rate in the firstrotor/stator stage is greater than the shear rate in subsequentstage(s). For example, in some embodiments, the shear rate in the firstrotor/stator stage is greater than or less than the shear rate in asubsequent stage(s). In other embodiments, the shear rate issubstantially constant along the direction of the flow, with the stageor stages being the same. If HSD 40 includes a PTFE seal, for example,the seal may be cooled using any suitable technique that is known in theart. The HSD 40 may comprise a shaft in the center which may be used tocontrol the temperature within HSD 40. For example, the slurry streamflowing in line 13 (or the liquid used to create the slurry ofcarbonaceous material) may be used to cool the seal and in so doing bepreheated as desired prior to entering the high shear device. Heat maybe added to HSD 40 (via the shaft or elsewhere, such as external to HSD40) to promote production of synthesis gas, in embodiments.

The rotor(s) of HSD 40 may be set to rotate at a speed commensurate withthe diameter of the rotor and the desired tip speed. As described above,the HSD (e.g., colloid mill or toothed rim disperser) has either a fixedclearance between the stator and rotor or has adjustable clearance.

HSD 40 serves to subject the slurry to high shear. In some embodimentsof the process, the transport resistance of the reactants is reduced byoperation of the high shear device such that the velocity of the one ormore reaction (i.e. production of synthesis gas) is increased by greaterthan a factor of about 5. In some embodiments, the velocity of thereaction is increased by at least a factor of 10. In some embodiments,the velocity is increased by a factor in the range of about 10 to about100 fold. In some embodiments, HSD 40 delivers at least 300 L/h at anominal tip speed of at least 22 m/s (4500 ft/min), 40 m/s (7900ft/min), and which may exceed 225 m/s (45,000 ft/min) or greater. Thepower consumption may be about 1.5 kW or higher as desired. Althoughmeasurement of instantaneous temperature and pressure at the tip of arotating shear unit or revolving element in HSD 40 is difficult, it isestimated that the localized temperature seen by the intimately mixedreactants may be in excess of 500° C. and at pressures in excess of 500kg/cm² under high shear conditions.

Conditions of temperature, pressure, space velocity, dispersible gas(line 22) composition, and slurry composition may be adjusted to producea desired product profile (and maintain safety). The use of HSD 40 mayallow for production of synthesis gas having a desirable H₂:CO ratio. Insome embodiments, the operating conditions of system 100 comprise atemperature of at or near ambient temperature and global pressure of ator near atmospheric pressure. If the carrier fluid/source of H₂ isliquefied, for example associated gas (natural gas), it may be moredesirable to operate the system at conditions under which the carrierfluid (e.g. the associated gas) remains a liquid and maintains aliquid/solid slurry with the solid (e.g., with the coal or otherhydrocarbonaceous material). Because the HSD 40 provides high pressure(e.g. 150,000 psi) at the tips of the rotors, the temperature of thereaction may be reduced relative to conventional gasification systems inthe absence of high shear. In embodiments, the operating temperature isless than about 70% of the conventional operating temperature, or lessthan about 60% of the conventional operating temperature, or less thanabout 50% of the conventional operating temperature for the samereaction(s)

The residence time within HSD 40 is typically low. For example, theresidence time can be in the millisecond range, can be about 10, 20, 30,40, 50, 60, 70, 80, 90 or about 100 milliseconds, can be about 100, 200,300, 400, 500, 600, 700, 800, or about 900 milliseconds, can be in therange of seconds, or can be any range thereamong.

Utilizing Synthesis Gas 600.

Process 300 may further comprise utilizing synthesis gas 600. Utilizingsynthesis gas 600 may comprise utilizing the synthesis gas or acomponent thereof (e.g. hydrogen) directly as a fuel or producing avalue product from the synthesis gas. It is noted that the method ofutilizing synthesis gas 601 may be utilized for the production ofproduct from any synthesis gas, not only for the production of productfrom synthesis gas obtained via high shear gasification of carbonaceousmaterials as described hereinabove. That is, another aspect of thisdisclosure is a method of producing product (e.g., comprising one ormore components selected from liquid hydrocarbons and alcohols) fromsynthesis gas obtained via any system and/or process. For example, thesynthesis gas may be provided by the herein disclosed gasification ofcarbonaceous materials via high shear, may be obtained via conventionalgasification (also called steam reforming) of carbonaceous material(e.g. coal, biomass, or natural gas), may be obtained via splitting ofnatural gas, may be obtained via partial combustion of hydrocarbons, ormay be obtained by some combination thereof.

In embodiments, synthesis gas produced in HSD 40 and/or obtained fromanother source/method is burned directly in internal combustion engines,used to produce methanol and hydrogen, or converted into productcomprising liquid hydrocarbons and/or alcohols. As indicated in FIG. 7,which is a schematic of a method of utilizing synthesis gas 601according to an embodiment of this disclosure, utilizing synthesis gasmay comprise separating synthesis gas from the high shear-treated stream700 and reacting the synthesis gas (which may further comprise carbondioxide) to produce products 800.

Separating Synthesis Gas from High Shear-Treated Stream 700.

A high shear-treated stream exits high shear device 40 at high shearoutlet line 19. High shear-treated stream 19 will typically comprisesynthesis gas; unreacted carbonaceous material; slurry liquid; andco-products including hydrocarbons that may be formed by reaction ofcarbonaceous material, e.g. by reaction of carbon monoxide and hydrogen(and catalysis by components of carbonaceous material), such co-productsincluding but not limited to C1-C4 compounds, CO, O₂, H₂O, and sulfurcompounds such as H₂S. Utilizing synthesis gas may comprise at step 700separating synthesis gas from high shear-treated stream 19. Utilizingsynthesis gas may comprise separating a product comprising synthesis gasfrom the high shear-treated stream. Separating a product comprisingsynthesis gas from the high shear-treated stream at 700 may compriseseparating synthesis gas and one or more co-products from the highshear-treated stream. Separating a product comprising synthesis gas fromthe high shear-treated stream at 700 may comprise separatingcarbonaceous material, slurry liquid, one or more co-products, or acombination thereof from the high shear-treated stream, leaving aproduct comprising synthesis gas.

Stream 19 may optionally enter vessel 10. Synthesis gas may be separatedfrom other components of high shear-treated stream 19 by any means knownin the art. Separating synthesis gas from high shear-treated stream inline 19 may comprise introducing the high shear-treated stream intovessel 10. As mentioned hereinabove, vessel 10 may be a separation unit,or may be more than one separation unit. Various components of highshear-treated stream 19 (e.g. product synthesis gas, one or moreco-products such as hydrocarbon products that may have formed within HSD40, slurry liquid, and unreacted carbonaceous material, e.g. coal) maybe extracted from vessel(s) 10 or can be extracted from one or moreseparation units downstream of vessel 10. Any suitable separation methodknown in the art may be used to separate the various components of highshear-treated stream 19. For example, one or more selected from vaporliquid separations, solid/liquid separations, distillations, and otherseparation means may be used to separate the desired components exitingHSD 40 and/or vessel 10.

In embodiments, synthesis gas product is removed via first vessel-10outlet line 16. The gas removed from vessel 10 via first vessel-10outlet line 16 may comprise other components in addition to synthesisgas, e.g. various amounts of carbon dioxide, methane, alcohols, hydrogensulfide and/or diesel. Slurry liquid and hydrocarbon product may beremoved via second vessel-10 outlet line 17. Unreacted carbonaceousmaterial may be removed from vessel 10 via third vessel-10 outlet line20. Alternatively, slurry liquid and unreacted carbonaceous material maybe removed together, e.g. via third vessel-10 outlet line 20. Vessel 10may comprise more than one separation unit as known in the art. Forexample, a liquid stream comprising liquid hydrocarbons produced in HSD40 and slurry liquid may be removed from vessel 10 or a first separationvessel and a second separation vessel may be used to separate the slurryliquid from the liquid hydrocarbons, in certain embodiments.

Separated slurry liquid and/or unreacted carbonaceous material may berecycled to HSD 40, for example by introduction into line 21, line 13,or HSD 40 via second vessel-10 outlet line 17 and/or third vessel-10outlet line 20.

Product synthesis gas, which may be extracted from vessel 10 via firstvessel-10 outlet line 16, may comprise hydrogen and carbon monoxide in adesired molar ratio, as discussed above. The synthesis gas may furthercomprise carbon dioxide and lower molecular weight hydrocarbons, e.g.methane. In embodiments, the product synthesis gas comprises less thanabout 50 mole percent, 40%, 30%, or 20% carbon dioxide. If hydrogen andsulfur are present in the HSD, H₂₅ can be formed. In embodiments, theproduct synthesis gas comprises less than about 20 mole percent, 10%, or5% hydrogen sulfide. As discussed hereinbelow, in embodiments (e.g., foruse with CO₂ sensitive FT catalyst) CO₂, H₂S, or other component of thesynthesis-gas containing stream removed from HSD 40 and/or vessel 10 canbe removed.

Reacting Synthesis Gas to Produce Products 800.

Utilizing synthesis gas may further comprise reacting synthesis gasunder suitable conditions to produce product 800. Step 800 may becatalytic and may comprise operating at Fischer-Tropsch (FT) operatingconditions. In embodiments, reacting synthesis gas to produce product800 comprises any means known in the art for reacting synthesis gas fromHSD 40 to produce FT hydrocarbons. The FT products may be formed asknown in the art, or may be produced utilizing a HSD, as describedhereinbelow, and/or as described in U.S. patent application Ser. No.12/138,269, now U.S. Pat. No. 8,133,925, which is hereby incorporatedherein in its entirety for all purposes not inconsistent with thisdisclosure.

A variety of synthesis gas compositions can be used for FT. Forcobalt-based catalysts the optimal H₂:CO ratio is around 1.8-2.1.Iron-based catalysts promote the water-gas-shift reaction and thus cantolerate significantly lower ratios. If the synthesis gas has arelatively low H₂:CO ratio (<1), iron catalyst may be desirable.Depending on the composition of the synthesis gas (produced in HSD 40 orobtained via other means), utilizing synthesis gas 601 may furthercomprise removing at least a portion of the sulfur and/orsulfur-containing compounds from the synthesis gas prior to step 800and/or removing at least a portion of the carbon dioxide from thesynthesis gas prior to step 800. For example, scrubbing (via one or morescrubbers) may be utilized to reduce the sulfur content of the resultingsyngas. Acid gas removal (via one or more acid gas removal units orAGRUs) may be utilized to reduce the carbon dioxide and/or hydrogensulfide content of the synthesis gas.

The Fischer-Tropsch process (or Fischer-Tropsch synthesis) is acatalyzed chemical reaction in which synthesis gas, a mixture of carbonmonoxide and hydrogen, is converted into liquid hydrocarbons of variousforms. The most common catalysts are based on iron and cobalt, althoughnickel and ruthenium have also been used. The principal purpose of thisprocess is to produce a synthetic petroleum substitute, typically fromcoal, natural gas or biomass, for use as synthetic lubrication oil or assynthetic fuel. This synthetic fuel runs trucks, cars, and some aircraftengines. The use of diesel is increasing in recent years.

The Fischer-Tropsch process involves a variety of competing chemicalreactions, which lead to a series of desirable products and undesirablebyproducts. The most important reactions are those resulting in theformation of alkanes. These can be described by chemical equations ofthe form:(2n+1)H₂ +nCO→C_(n)H_((2n+2)) +nH₂O  (7)

where n is a positive integer. The simplest of these (n=1), results information of methane, which is generally considered an unwantedbyproduct (particularly when methane is the primary feedstock used toproduce the synthesis gas). Process conditions and catalyst compositionare usually chosen to favor higher order reactions (n>1) and thusminimize methane formation. Most of the alkanes produced tend to bestraight-chained, although some branched alkanes are also formed. Inaddition to alkane formation, competing reactions result in theformation of alkenes, as well as alcohols and other oxygenatedhydrocarbons. Usually, only relatively small quantities of thesenon-alkane products are formed, although catalysts favoring some ofthese products have been developed.

Another important reaction is the water gas shift reaction, WGSR, (6)hereinabove. Although the WGS reaction results in formation of unwantedCO₂, it can be used to shift the H₂:CO ratio of the incoming synthesisgas. This will be desirable if the synthesis gas utilized in step 800has a ratio of about 0.7. If the mole ratio of hydrogen to carbonmonoxide is higher, e.g. about 2, catalyst that does not promote WGSRmay be utilized. The water gas shift reaction is sensitive totemperature, with the tendency to shift towards reactants as temperatureincreases due to Le Chatelier's principle.

It should be noted that, according to published data on the currentcommercial implementations of the coal-based Fischer-Tropsch process,these plants can produce as much as 7 metric tons of CO₂ per metric tonof liquid hydrocarbon products (excluding the reaction water product).This is due in part to the high energy demands required by thegasification process, and in part by the design of the process asimplemented. Utilization the process disclosed herein may allowproduction of reduced amounts of CO₂ and/or conversion of the CO₂ toproduct (e.g., alcohols).

In embodiments, step 800 comprises catalytically reacting synthesis gasunder FT operating conditions to produce FT product and utilizes typicalFT operating temperatures in the temperature range of 150-300° C.(302-572° F.). Generally, higher temperatures lead to faster reactionsand higher conversion rates, but also tend to favor methane production.The use of an HSD 40 a, as described below, may allow the use of lowerthan conventional FT operating temperatures, and reduced undesirablemethane production. The temperature for catalytically reacting synthesisgas under FT operating conditions to produce FT product may bemaintained at the low to middle part of the above range. Increasing thepressure generally leads to higher conversion rates and also favorsformation of long-chained alkanes both of which are desirable. Typicalpressures are in the range of one to several tens of atmospheres.Chemically, even higher pressures would be favorable, but the benefitsmay not justify the additional costs of high-pressure equipment. The useof HSD 40 a, as discussed below, may enable more desirable productdistribution, due to the high local pressure provided by the HSD.

In general the product distribution of hydrocarbons formed during theFischer-Tropsch process follows an Anderson-Schulz-Flory distribution,which can be expressed as:W _(n) /n=(1−α)²α^(n−1).  (8)where W_(n) is the weight fraction of hydrocarbon molecules containing ncarbon atoms, α is the chain growth probability or the probability thata molecule will continue reacting to form a longer chain. In general,alpha, α, is largely determined by the catalyst and the specific processconditions.

Examination of Eq. (8) reveals that methane will typically be thelargest single product, however by having α approach one, the totalamount of methane formed can be minimized compared to the sum of all ofthe various long-chained products. Increasing α increases the formationof long-chained hydrocarbons. The very long-chained hydrocarbons arewaxes, which are solid at room temperature. Therefore, for production ofliquid transportation fuels it may be necessary to crack some of theFischer-Tropsch products, via downstream processing. In order to avoidthis, zeolites or other catalyst substrates with fixed sized pores thatcan restrict the formation of hydrocarbons longer than somecharacteristic size (usually n<10) may be utilized.

In embodiments, conventional FT is used to produce FT products from thesynthesis gas produced in HSD 40. Alternatively, FIG. 8 is a schematicof a method of reacting synthesis gas from HSD 40 or obtained by anyother means known in the art to produce products comprising hydrocarbonsand/or alcohols 801 according to an embodiment of this disclosure.Reacting synthesis gas to produce products 801 comprises producing adispersion of synthesis gas in a liquid phase 802, introducing thedispersion into a vessel 803, and extracting product 804.

Producing Dispersion of Synthesis Gas in Liquid Phase 802.

Reacting synthesis gas to produce products 801 may be used inconjunction with the method 300 of producing synthesis gas fromcarbonaceous slurry or may be a stand-alone method suitable to formproduct comprising one or more of liquid hydrocarbons and/or alcoholsfrom synthesis gas (which may comprise other gaseous components, e.g.carbon dioxide, as discussed further hereinbelow) obtained by any meansknown in the art. Method 801 comprises producing a dispersion ofsynthesis gas in a liquid phase 802. Producing a dispersion of synthesisgas in liquid phase 802 may comprise introducing the product synthesisgas from HSD 40 and/or synthesis gas from another source/method into aHSD 40 a. In embodiments, vessel 10 (or additional separation unitsdownstream vessel 10) serves to separate product synthesis gas fromliquid hydrocarbons produced in HSD 40, unreacted carbonaceousmaterials, and slurry liquid. In such embodiments a portion 22 a of thesynthesis gas removed from vessel 10 via first vessel-10 outlet line 16can be combined with liquid carrier in line 21 a and pumped via line 13a and pump 5 a into (second) HSD 40 a. In embodiments, producthydrocarbons from HSD 40 and synthesis gas produced in HSD 40 areremoved together from vessel 10 via first vessel-10 outlet line 16. Insuch embodiments, the hydrocarbons produced in HSD 40 may serve asliquid carrier and little or no additional liquid carrier may beintroduced via line 21 a.

Producing dispersion of synthesis gas in liquid phase 802 comprisesintroducing product synthesis gas from HSD 40 and/or synthesis gasobtained via another method or source into HSD 40 a along with liquidcarrier. The liquid carrier and synthesis gas may be introducedseparately to HSD 40 a, or may be combined prior to introduction thereto(e.g. when removed from vessel 10 together). HSD 40 a serves to producea dispersion of synthesis gas in the liquid carrier, operating asdiscussed above with respect to operation of HSD 40, but at conditionssuitable for conversion of synthesis gas rather than at conditionssuitable for gasification of carbonaceous materials as in HSD 40. Thehigh shear produced within HSD 40 a results in dispersion of thesynthesis gas (and optionally carbon dioxide) in micron orsubmicron-sized bubbles or droplets within a continuous liquid phase.The liquid phase may comprise liquid FT hydrocarbons, alcohols, or othersuitable liquid carrier. In some embodiments, the resultant dispersionproduced in HSD 40 a has an average bubble size less than about 5, 4, 3,2, 1.5, or 1 μm. Accordingly, the dispersion exiting HSD 40 a via line19 a comprises micron and/or submicron-sized synthesis gas bubbles. Insome embodiments, the mean bubble size is in the range of about 0.4 μmto about 1.5 μm. In some embodiments, the resultant dispersion has anaverage bubble or droplet size less than or about 1 μm. In someembodiments, the mean bubble size is less than about 400 nm, and may beless than or about 100 nm in some cases. In many embodiments, themicrobubble dispersion is able to remain dispersed at atmosphericpressure for at least 15 minutes.

Introducing Dispersion into Vessel 803.

Reacting synthesis gas to produce product 801 may further compriseintroducing the dispersion into a vessel 802. Once dispersed, theresulting dispersion exits HSD 40 a via line 19 a and may be introducedinto a second vessel 10 a, as illustrated in FIG. 5. As a result of theintimate mixing of the reactants prior to entering vessel 10 a, asignificant portion of the reactions may take place in HSD 40 a.Catalyst, e.g. FT catalyst and/or catalyst designed to promote theproduction of alcohol, may be present within synthesis gas utilizationapparatus 30. In embodiments, FT catalyst, as described above, may becoated onto portions of HSD 40 a or may be introduced into HSD 40 a withliquid carrier, e.g. via line 21 a. Accordingly, in some embodiments,reactor/vessel 10 a may be used primarily for heating and separation ofproducts from unreacted synthesis gas. In embodiments, vessel 10 a isabsent. Alternatively, or additionally, vessel 10 a may serve as aprimary reaction vessel where most of the product is produced.Vessel/reactor 10 a may be operated in either continuous orsemi-continuous flow mode, or it may be operated in batch mode. Thecontents of vessel 10 may be maintained at a specified reactiontemperature using heating and/or cooling capabilities (e.g., coolingcoils) and temperature measurement instrumentation, employing techniquesthat are known to those of skill in the art. Pressure in the vessel maybe monitored using suitable pressure measurement instrumentation, andthe level of reactants in the vessel may be controlled using a levelregulator, employing techniques that are known to those of skill in theart. Vessel 10 a may be configured as a slurry bed reactor, a fluidizedbed reactor, or a fixed bed reactor.

Extracting Product 804.

Reacting synthesis gas to produce product 801 may further compriseextracting product(s) 804. The reaction product(s) may be extracteddirectly from HSD 40 a (e.g., when HSD 40 a or liquid carrier 21 acontains catalyst). Alternatively or additionally, product may beextracted from vessel 10 a or a separation vessel downstream thereof.For example, unreacted synthesis gas (and lighter hydrocarbon products,such as, but not limited to, methane, alcohols and diesel) may beremoved from vessel 10 a via first vessel-10 a outlet line 16 a andliquid product may be removed from vessel 10 a via second vessel-10 aoutlet line 17 a. In embodiments, catalyst is circulated aboutproduction apparatus 30 (and HSD 40 a), and catalyst may be separatedfrom the product and recycled, for example, by introduction into liquidcarrier line 21 a or recycle directly into vessel 10 a. The unreactedsynthesis gas and other light gas extracted via first vessel-10 a outletline 16 a may be recycled to HSD 40 a, for example, via dispersiblesynthesis gas line 22 a. Product exiting system 100 via line 19 a orsecond vessel-10 a outlet line 17 a may be upgraded, sold, and orutilized as known in the art.

HSD 40 a may be operated such that the reaction product extracted at 804comprises alcohols and/or liquid hydrocarbons. In embodiments, thereaction product comprises substantially equal amounts of liquidhydrocarbons and alcohols. In such embodiments, product hydrocarbons andalcohols can be separated as known in the art. Conventional GTLtypically produces significant amounts of water and relatively lowamounts (e.g., 3-5%) of alcohol. In embodiments, product extracted (fromHSD 40 a and/or vessel 10 a) comprises less water and/or more alcoholsthan conventional GTL product. The disclosed high shear synthesis gasutilization method may allow production of significant amounts ofalcohol and low amounts (e.g., 3-5% or less than about 10%) of water.

In embodiments, synthesis gas from HSD 40 (produced from high sheargasification of carbonaceous material as described herein) and/orsynthesis gas from another source/method is converted as described aboveto product comprising alcohols and hydrocarbons. In embodiments, theproduct from HSD 40 a comprises hydrocarbons as a major component,alcohols as a secondary component, and water as a minor component. Inembodiments, the product comprises greater than about 90% of componentsselected from alcohols and liquid hydrocarbons and less than about 10%water (for example, about 97% alcohols and/or hydrocarbons and about 3%water). Without wishing to be limited by theory, due to the conditionsto which the gas is subjected within the HSD, significant amounts ofalcohols may be produced in HSD 40 a, with concomitant production ofless water than conventional GTL. Carbon dioxide in the gas fed to HSD40 a may be converted to alcohols, rather than reacting with hydrogen toproduce excess water. In this manner, value may be obtained from CO₂ inthe feed synthesis gas. Thus, removal of carbon dioxide from synthesisgas prior to HSD 40 a may thus be unnecessary and/or undesirable. Inembodiments, available CO₂ may even be fed into the HSD 40 a along withsynthesis gas. Without wishing to be limited by theory, the extremepressures/shear produced at the tips of the rotor/stator is believed toforce the reaction away from the thermodynamically expected productionof water toward the production of alcohols.

Conventional GTL processes typically produce a maximum of 27-28 moles ofliquid product per 100 moles of gas fed. In embodiments, greater than 28mole of liquid product comprising alcohols and/or liquid hydrocarbons isproduced by high shear utilization of synthesis gas (and optionallycarbon dioxide) as disclosed herein.

Liquid hydrocarbons and/or alcohols removed from vessel 10 may becombined with liquid product comprising liquid hydrocarbons and/oralcohols in line 17. A portion of the product in line 17 a may beseparated and utilized as liquid carrier upon recycle to HSD 40 a vialine 21 a. Line 21 a may thus contain a flowing fresh carrier streamand/or a recycle stream from vessel 10 a. As mentioned above withrespect to conventional FT hydrocarbon production, the productdistribution will be dependent on operating conditions, any catalystutilized, and feed gas (synthesis gas and/or carbon dioxide)composition. In embodiments, the product comprises hydrocarbons havingprimarily C5+ hydrocarbon products (i.e., hydrocarbons having five ormore carbons).

Catalyst (e.g., FT catalyst and/or catalyst designed to promoteproduction of alcohols from synthesis gas comprising carbon dioxide) maybe introduced directly into vessel 10 a, as a hydrocarbon slurry orstream. Alternatively, or additionally, catalyst may be added elsewherein system 100. For example, catalyst slurry may be injected into line 21a.

Commonly known FT operating conditions may be utilized in HSD 40 a andvessel 10 a. Alternatively, less severe operating conditions (i.e. lowertemperature and/or pressure) may be utilized in product productionapparatus 30.

Multiple Pass Operation.

In the embodiment shown in FIG. 5, the system is configured for singlepass operation. The output of HSD 40 may be run through a subsequentHSD. In some embodiments, it may be desirable to pass the contents offlow line 19, or a fraction thereof, through HSD 40 during a secondpass. In this case, at least a portion of the contents of flow line 19may be recycled from flow line 19 and pumped by pump 5 into line 13 andthence into HSD 40. Additional reactants may be injected via line 22into line 13, or may be added directly into the HSD. In otherembodiments, product is further treated prior to recycle of a portionthereof to HSD 40. Similarly, where suitable, multiple pass operationmay be utilized for stand-alone or integrated HSD 40 a (i.e., whetherHSD 40 a is utilized along with HSD 40 or for conversion of gas obtainedby means other than high shear gasification of carbonaceous materialsvia HSD 40).

Multiple HSDs.

In some embodiments, two or more HSDs like HSD 40, or configureddifferently, are aligned in series, and are used to promote furtherreaction. Operation of the mixers may be in either batch or continuousmode. In some instances in which a single pass or “once through” processis desired, the use of multiple HSDs in series may also be advantageous.In embodiments, the reactants pass through multiple HSDs 40 in serial orparallel flow. For example, in embodiments, product in outlet line 19 isfed into a second HSD. When multiple HSDs 40 are operated in series,additional reactants (liquid, gaseous or solid) may be injected into theinlet feedstream of each HSD. For example, additional dispersible gas orvapor, such as hydrogen, oxygen, air, associated gas or steam may beintroduced into a second or subsequent HSD 40. In some embodiments,multiple HSDs 40 are operated in parallel, and the outlet productstherefrom are introduced into one or more flow lines 19. Similarly,multiple HSDs 40 a may be utilized, where suitable, and additionalreactants (e.g., synthesis gas and/or carbon dioxide) or carrier may beintroduced, as desired, into additional HSDs 40 a.

Features.

The rate of chemical reactions involving liquids, gases and solidsdepend on time of contact, temperature, and pressure. In cases where itis desirable to react two or more raw materials of different phases(e.g. solid and liquid; liquid and gas; solid, liquid and gas; solid andgas), one of the limiting factors controlling the rate of reactioninvolves the contact time of the reactants. When reaction rates areaccelerated, residence times may be decreased, thereby increasingobtainable throughput.

In the case of heterogeneously catalyzed reactions there is theadditional rate limiting factor of having the reacted products removedfrom the surface of the solid catalyst to permit the catalyst tocatalyze further reactants. Contact time for the reactants and/orcatalyst is often controlled by mixing which provides contact withreactants involved in a chemical reaction. The use of the disclosedHSD(s) may increase rates of reaction relative to conventional systemsand methods. For example, gasification of carbonaceous material and/orthe rate of FT reaction may be increased via the disclosed system andmethod.

Not to be limited by theory, it is known in emulsion chemistry thatsub-micron particles, or bubbles, dispersed in a liquid undergo movementprimarily through Brownian motion effects. Such sub-micron sizedparticles or bubbles may have greater mobility through boundary layersof solid catalyst particles, thereby facilitating and accelerating thecatalytic reaction through enhanced transport of reactants.

The intimate contacting of reactants provided by the HSDs may result infaster and/or more complete reaction of reactants [e.g., CH_(x) and H₂Ovia Eqs. (3)/(5) and/or the reaction of CO and H₂ according to Eq. (7)].In embodiments, use of the disclosed process comprising reactant mixingvia external HSD allows use of reduced quantities of catalyst (e.g. FTcatalyst) than conventional configurations and methods and/or increasesthe product yield and/or the conversion of reactants (e.g. carbon in thecarbonaceous material of the slurry in HSD 40 and synthesis gas withinHSD 40 a). In embodiments, the method comprises incorporating anexternal HSD into an established process thereby reducing the amount ofcatalyst required to effect desired reaction and/or enabling an increasein production throughput from a process operated without a HSD. Forexample, incorporation of one or more HSDs 40 into an existing FTproduction plant may reduce costs and/or increase production of liquidhydrocarbon products by allowing more economical production of synthesisgas having a desired composition. The incorporation of a HSD forproduction of synthesis gas may reduce the amount of processing of thesynthesis gas required upstream of a conventional FT reactor (e.g.,reduce or eliminate the need for removal of CO₂ from the synthesis gasprior to FT). In embodiments, the disclosed method reduces operatingcosts and/or increases production from an existing process.Alternatively, the disclosed method may reduce capital costs for thedesign of new processes.

Without wishing to be limited to a particular theory, it is believedthat the HSD of certain embodiments of the present system and methodsmay induce cavitation whereby one or more reactant is dissociated intofree radicals, which then react. In embodiments, the extreme pressure atthe tips of the rotors/stators leads to liquid phase reaction, and nocavitation is involved.

Use of Multifunctional Catalysts.

In some embodiments, multifunctional catalyst is used in the processesdescribed herein. In an embodiment, the multifunctional catalyst is ableto promote both dehydrogenation reactions and alcohol forming (AF)reactions. In another embodiment, the multifunctional catalyst iscapable of promoting both FT reactions and alcohol forming (AF)reactions. In some embodiments, the multifunctional catalyst is a blendof dehydrogenation catalyst and AF catalyst. In some other embodiments,the multifunctional catalyst is a blend of FT catalyst and AF catalyst.Catalysts for dehydrogenation reactions, FT reactions, and alcoholforming (AF) reactions are disclosed herein and are also known in theart. The disclosures of U.S. Patent Application Pub. No. 2008/0281136and U.S. Pat. Nos. 5,659,090 and 4,551,444 are hereby incorporatedherein by reference for further details concerning dehydrogenationcatalysts, FT catalysts, and AF catalysts.

Depending on the feedstock and desired end products, variousmultifunctional catalysts may be used. Such catalysts are capable ofpromoting catalytic processes such as dehydrogenation, waterdissociation, carbon dioxide dissociation, syngas reforming, and alcoholsynthesis. For example, a multifunctional catalyst is used in a FTprocess, wherein said catalyst promotes dissociation/oxidation of a fuelto produce syngas and also syngas reforming reactions. In some cases,such multifunctional catalyst is a blend formed by intimate mixing ofseveral suitable and compatible catalysts. In some other cases, suchmultifunctional catalyst is a mixture, comprising separate catalystparticles. Combinations of inorganic and organic catalysts (includingbiocatalysts) can also be used.

In some embodiments, the use of multifunctional catalyst for FTreactions and AF reactions reduces the production of unwantedby-products (e.g., water, carbon monoxide, carbon dioxide). In someembodiments, the use of multifunctional catalyst for FT reactions and AFreactions enhances the production of C2+ hydrocarbons and oxygenates(e.g., alcohols). In some embodiments, the use of multifunctionalcatalyst for dehydrogenation reactions and AF reactions reduces theproduction of unwanted by-products (e.g., water, carbon monoxide, carbondioxide). In some embodiments, the use of multifunctional catalyst fordehydrogenation reactions and AF reactions enhances the production ofC2+ hydrocarbons and oxygenates (e.g., alcohols).

In an embodiment, a multifunctional catalyst is utilized, wherein saidmultifunction catalyst is capable of (1) splitting methane(dehydrogenating or partially oxidizing methane); (2) syngas reforming;(3) alcohol synthesis; and (4) dissociating water and/or carbon dioxide.In some cases, such multifunctional catalyst is a blend formed byintimate mixing of several suitable and compatible catalysts. In someother cases, such multifunctional catalyst is a mixture, comprisingseparate catalyst particles. Multiple HSD's may be utilized in series toperform different reactions. Some HSD's use suitable catalysts; someHSD's do not need the presence of catalysts. In the reactions thatinvolve carbon dioxide, in some cases, carbon dioxide is dissolved inwater to become carbonic acid (H₂CO₃) before dissociation.

In some embodiments, the multifunctional catalyst is applied in a fixedbed reactor. For example, the fixed bed reactor is downstream of theHSD. After the reactants are intimately mixed in the HSD, the reactantmixture is introduced into the fixed bed reactor comprising themultifunctional catalyst and reactions are allowed to propagate in thefixed bed reactor. In some other embodiments, the multifunctionalcatalyst is applied as a slurry. For example, multifunctional catalystslurry and reactants may be mixed in the HSD and then the reactantmixture with the catalyst slurry is introduced into a suitable vessel.Reactions may take place in both the HSD and the vessel. In some furtherembodiments, the multifunctional catalyst is applied by beingconstructed as a catalytic surface in the HSD. For example, reactantsare introduced into a HSD comprising a catalytic surface containingmultifunctional catalyst. Reactions are initiated in the HSD and allowedto propagate in a suitable vessel fluidly connected to the HSDdownstream.

In some embodiments, additional carbon dioxide and/or water is needed inthe processes utilizing multifunctional catalysts so that desiredproducts are obtained. For example, when multiple HSD's are used (inparallel or in series), carbon dioxide and/or water may be addedinter-stage where necessary. It is contemplated that one of ordinaryskill in the art, provided this disclosure, is able to make suchjudgments as to where additional reactants (e.g., carbon dioxide and/orwater) are needed.

EXAMPLES

Various dimensions, sizes, quantities, volumes, rates, and othernumerical parameters and numbers have been used for purposes ofillustration and exemplification of the principles of the invention, andare not intended to limit the invention to the numerical parameters andnumbers illustrated, described or otherwise stated herein. Likewise,unless specifically stated, the order of steps is not consideredcritical. The different teachings of the embodiments discussed below maybe employed separately or in any suitable combination to produce desiredresults.

Example 1 High Shear Reaction of 2:1 Methane:Carbon Dioxide withRuthenium Carbonyl

A cold trap was positioned within system 100 as shown in FIG. 1. Five(5) grams of tri-ruthenium carbonyl was dissolved at 125° C. in ½L ofPEG. This ruthenium carbonyl/PEG was added to 1 L PEG. Three hours afterinitiation of the test, ruthenium carbonyl/PEG solution was injectedinto vessel 10 for a period of one hour.

Liquid product MBM-33-B (Liquid) was recovered from cold trap liquid 24and analyzed for glycols. The results are presented in Table 2.

TABLE 2 MBM 33B (Liquid) Test Method Component Amount, mg/L SW-846 8015DNon Purgeable Ethanol 484 Organic Compounds Methanol 4637 n-PropylAlcohol 44.7 t-Butyl Alcohol 7.08 SW-846 8015M Glycols Ethylene Glycol27264 Diethylene Glycol 68170 Triethylene Glycol 123207 Tetraethyleneglycol 142359 SW-846 8260B Volatile Organic 1,2,4- 0.826 CompoundsTrimethylbenzene 1,3,5- 0.574 Trimethylbenzene Ethylbenzene 0.193 m- &p-Xylenes 1.04 MEK 18.6 Naphthalene 0.601 n-Butylbenzene 0.143 o-Xylene0.570 Xylenes 1.61 TX 1005 C₆-C₁₂ 407 Total PetroleumHydrocarbons >C12-C28 343 >C28-C35 BRL* Total C6-C35 750 TX 1006 TotalPetroleum Aliphatic (>C06-C08) BRL Hydrocarbons Aliphatic (>C08-C10) BRLAliphatic (>C10-C12) BRL Aliphatic (>C12-C16) 139.656 Aliphatic(>C16-C21) 53.404 Aliphatic (>C21-C35) BRL Aromatic (C06-C08) BRLAromatic (C08-C10) 478.062 Aromatic (C10-C12) 54.089 Aromatic (C12-C16)50.074 Aromatic (C16-C21) 61.368 Aromatic (C21-C35) BRL *BRL: BelowRecordable Limits

Example 2 High Shear Reaction of 2:1 Methane:Carbon Dioxide withRuthenium Carbonyl

Sample MBM 34-2 was taken from cold trap gas 25, sample 34-1 from vessel10 product liquid 16, and sample 34-PEG was a sample of virginpolyethylene glycol. The results were analyzed for hydrocarbons andglycols, and the results are presented in Table 3.

TABLE 3 MBM 34-1, MBM 34-2, and MBM 34 PEG MBM 34-1 MBM 34-2 MBM 34-Reactor Cold Trap PEG Test Method Component Liquid Gas Virgin PEG EPATO-15 Volatile Benzene — 2.72 — Organic Compounds in Air Toluene — 3.51— by GCMS, nL Ethylbenzene — 7.55 — m- & p-Xylenes — 8.81 — Styrene —1.09 — o-Xylene — 9.17 — 1,3,5- — 2.68 — Trimethylbenzene 1,2,4- — 5.74— Trimethylbenzene SW-846 8015D Non Ethanol BRL* — BRL Purgeable OrganicMethanol BRL — BRL Compounds, mg/kg n-Propyl Alcohol BRL — BRL t-ButylAlcohol BRL — BRL SW-846 8015M Glycols, Ethylene Glycol 2780 — BRL mg/kgDiethylene Glycol 27216 — 27353 Triethylene Glycol 152328 — 165424Tetraethylene glycol 402944 — 430688 SW-846 8260B Volatile 1,2,4- 0.460— 0.163 Organic Compounds, Trimethylbenzene mg/kg 1,3,5- 0.128 — 0.097Trimethylbenzene Ethylbenzene 0.139 — 0.329 m- & p-Xylenes 0.574 — 0.509MEK 0.210 — 0.490 Naphthalene BRL — BRL n-Butylbenzene BRL — BRLn-Propylbenzene — — 0.059 o-Xylene 0.249 — 0.097 Xylenes — — — Toluene0.131 — 0.701 TX 1005 C₆-C₁₂ 1457 — 497 Total Petroleum >C12-C28 3531 —1950 Hydrocarbons, mg/kg >C28-C35 BRL — BRL Total C6-C35 4988 — 2447 TX1006 Total Petroleum Aliphatic (>C12-C16) BRL — BRL Hydrocarbons, mg/kgAliphatic (>C16-C21) BRL — BRL Aromatic (C8-C10) 342.049 — 339.020Aromatic (C10-C12) 1569.564 — 1229.302 Aromatic (C12-C16) 994.041 —866.937 Aromatic (C16-C21) 1566.368 — BRL *BRL: Below Recordable Limits

Samples MBM-34D and MBM-34F were taken from the cold trap liquid 24, asdescribed in Appendix A attached herewith. The results of the analysisthereof are presented in Table 4.

TABLE 4 MBM 34-1, MBM 34-2, and MBM 34 MBM 34-D MBM 34-F Test MethodComponent Cold Trap Cold Trap SW-846 8015D Non Ethanol 146 125 PurgeableOrganic Methanol 2020 2884 Compounds, mg/L n-Propyl Alcohol 13.9 20.9t-Butyl Alcohol BRL* BRL SW-846 8015M Ethylene Glycol 11363 13147Glycols, mg/L Diethylene Glycol 34752 31944 Triethylene Glycol 5141754701 Tetraethylene glycol 64274 104596 SW-846 8260B 1,2,4- 0.258 BRLVolatile Organic Trimethylbenzene Compounds, mg/L 1,3,5- BRL BRLTrimethylbenzene Ethylbenzene BRL BRL m- & p-Xylenes 0.260 BRL MEK 11.64.29 Naphthalene 0.156 BRL n-Butylbenzene BRL BRL n-Propylbenzene BRLBRL o-Xylene 0.142 BRL Xylenes 0.402 BRL Toluene BRL BRL TX 1005 C₆-C₁₂231 354 Total Petroleum >C12-C28 116 3156 Hydrocarbons, >C28-C35 BRL BRLmg/L Total C6-C35 347.583 3510 TX 1006 Total Aliphatic (>C6-C8) BRL BRLPetroleum Aliphatic (>C8-C10) BRL BRL Hydrocarbons, mg/L Aliphatic(>C10-C12) BRL BRL Aliphatic (>C12-C16) 54.754 1447.8 Aliphatic(>C16-C21) 36.737 774.1 Aliphatic (>C21-C35) BRL 533.8 Aromatic (C6-C8)BRL BRL Aromatic (C8-C10) 112.049 BRL Aromatic (C10-C12) 37.385 BRLAromatic (C12-C16) 35.599 251.4 Aromatic (C16-C21) 47.699 403.0 Aromatic(C21-C35) BRL BRL *BRL: Below Recordable Limits

Example 4 High Shear Reaction of 2:1 Methane:Carbon Dioxide and MethaneAlone in Paraffinic Oil with Palladium Silica Catalyst

Samples MBM-35B Water and 35-TagA Water were taken from the cold trap 24as indicated in Appendix A hereinbelow. The results of the analysisthereof are presented in Table 5.

TABLE 5 MBM 35-B Water and MBM 35-TagA Water MBM MBM 35-B 35- Cold TagACold Cold Trap Trap Test Method Component Liquid Liquid SW-846 8015DNon- 2-Propanol BRL* BRL Purgeable Organic Ethanol 2648 2036 Compounds,mg/L Isobutyl Alcohol 66.9 41.4 Methanol 1147 1602 n-Butanol 881 828n-Propyl Alcohol 1488 1180 sec-Butyl Alcohol 474 447 t-Butyl Alcohol58.4 72.5 SW-846 8015M Ethylene Glycol 2761 2846 Glycols, mg/LDiethylene Glycol 2842 4747 Triethylene Glycol 2568 4367 Tetraethyleneglycol 774 1644 SW-846 8260B Volatile 1,2,4- BRL BRL Organic Compounds,Trimethylbenzene mg/L 1,3,5- BRL BRL Trimethylbenzene Ethylbenzene BRLBRL m- & p-Xylenes BRL BRL MEK 386 783 Naphthalene BRL BRLn-Butylbenzene BRL BRL n-Propylbenzene BRL BRL o-Xylene BRL BRL XylenesBRL BRL Toluene BRL BRL TX 1005 C₆-C₁₂ 1556 1255 TotalPetroleum >C12-C28 3655 2460 Hydrocarbons, mg/L >C28-C35 931 1418 TotalC6-C35 6142 5133 TX 1006 Total Aliphatic (>C6-C8) BRL BRL PetroleumAliphatic (>C8-C10) 38.4 61.7 Hydrocarbons, mg/L Aliphatic (>C10-C12)92.2 121.7 Aliphatic (>C12-C16) 549.3 387.7 Aliphatic (>C16-C21) 733.7561.9 Aliphatic (>C21-C35) 3281.5 3759.2 Aromatic (C6-C8) 456.5 414.8Aromatic (C8-C10) 617.1 321 Aromatic (C10-C12) 690.8 248 Aromatic(C12-C16) 701.4 118.6 Aromatic (C16-C21) 162.5 BRL Aromatic (C21-C35)87.7 BRL *BRL: Below Recordable Limits

Samples MBM-35B Oil and MBM-35TagA Oil both were taken from vessel 10liquid, as indicated in Appendix A attached herewith. The results of theanalysis thereof are presented in Table 6.

TABLE 6 MBM 35-B Oil and MBM 35-TagA Oil MBM MBM 35-B 35-TagA Oil- OilVessel 10 Vessel 10 Test Method Component Liquid Liquid SW-846 8015DNon- 2-Propanol BRL* BRL Purgeable Organic Ethanol 450 202 Compounds,mg/kg Isobutyl Alcohol 71.8 38.9 Methanol 132 173 n-Butanol 1611 818n-Propyl Alcohol 867 378 sec-Butyl Alcohol 361 174 t-Butyl Alcohol BRLBRL SW-846 8015M Ethylene Glycol BRL BRL Glycols, mg/kg DiethyleneGlycol BRL BRL Triethylene Glycol BRL BRL Tetraethylene glycol BRL BRLSW-846 8260B Volatile 1,2,4- BRL BRL Organic Compounds, Trimethylbenzenemg/kg 1,3,5- BRL BRL Trimethylbenzene Ethylbenzene BRL BRL m- &p-Xylenes BRL BRL MEK 462 545 Naphthalene BRL BRL n-Butylbenzene BRL BRLn-Propylbenzene BRL BRL o-Xylene BRL BRL Xylenes BRL BRL Toluene BRL BRLTX 1005 C₆-C₁₂ 160598 19135 Total Petroleum >C12-C28 534858 60488Hydrocarbons, mg/kg >C28-C35 128928 47059 Total C6-C35 824384 126682 TX1006 Total Aliphatic (>C6-C8) BRL BRL Petroleum Aliphatic (>C8-C10)14144 BRL Hydrocarbons, mg/kg Aliphatic (>C10-C12) 24985 3160.8Aliphatic (>C12-C16) 78792 8115.5 Aliphatic (>C16-C21) 100170 11078.6Aliphatic (>C21-C35) 484242 78233.2 Aromatic (C06-C08) 15842 10369.9Aromatic (C08-C10) 55048 11291.5 Aromatic (C10-C12) 67800 8445.2Aromatic (C12-C16) 73365 6187.8 Aromatic (C16-C21) 25389 3866.2 Aromatic(C21-C35) BRL BRL *BRL: Below Recordable Limits

Example 5 High Shear Ethane Conversion

For this example, the same equipment configuration as used in examples2-4 was utilized. The agitator on vessel 10 was operated at 1000 RPM.The High Shear unit 40 was operated at 13,500 RPM. The vessel 10 washeld at 150° C. and 345 kPa (50 psi).

Six liters of melted polyethylene glycol having a number averagemolecular weight, M_(n), of 850-950 (Sigma Aldrich) was placed in vessel10 along with 2 kilograms of Palladium Catalyst (0.5 wt. % Pd on SiO₂)and 5 grams of Triruthenium Dodecacarbonyl (Sigma Aldrich). All 3heaters (H1, H2, H3), gear pump 5 and HSD 40 were turned on.

System 100 was closed and purged with CO₂ three times and the gascompressor (extracting gas from the top of vessel 10 to inlet line 22 ofHSD 40) was turned on. Gas feed comprising ethane and CO₂ at anapproximate flow ratio of 2:1 was introduced into top of vessel 10.Similar runs were conducted with and without injection of 1 L of waterinto vessel 10. After 12 hours, the experiment was terminated andsamples were taken from cold trap 30 and analyzed. Results are presentedin Table 7, MBM 39-A results are without water injection, and MBM 39-AWare with water injection.

TABLE 7 MBM 39-A and MBM 39-AW Cold Trap Liquid MBM Test MethodComponent MBM 39-A 39-AW SW-846 8015D Non- 2-Propanol BRL* BRL PurgeableOrganic Ethanol 3876 77.9 Compounds, mg/L Isobutyl Alcohol BRL BRLMethanol 3938 180 n-Butanol BRL BRL n-Propyl Alcohol 339 BRL sec-ButylAlcohol BRL BRL t-Butyl Alcohol 44.4 BRL SW-846 8015M Ethylene Glycol2142 156 Glycols, mg/L Diethylene Glycol 2785 94.2 Triethylene Glycol284 BRL Tetraethylene glycol 707 BRL SW-846 8260B Volatile MEK 176 4.47Organic Compounds, mg/L TX 1005 C₆-C₁₂ BRL 70.1 Total Petroleum >C12-C2814609 1031 Hydrocarbons, mg/L >C28-C35 BRL BRL Total C6-C35 14609 1101.1*BRL: Below Recordable Limits

Example 6 High Shear Propane Conversion

A run with conditions and equipment similar to Example 5 was conductedwith propane gas substituted for ethane. Similar runs were conductedwith and without injection of 1 L of water into vessel 10. After 12hours, the experiment was terminated and samples were taken from coldtrap 30 and analyzed. Results are presented in Table 8, MBM 39-B resultsare without water injection, and MBM 39-BW are with water injection.

TABLE 8 MBM 39-B and MBM 39-BW Cold Trap Liquid MBM Test MethodComponent MBM 39-B 39-BW** SW-846 8015D Non- 2-Propanol BRL* BRLPurgeable Organic Ethanol 569 47.1 Compounds, mg/L Isobutyl Alcohol BRLBRL Methanol 5949 482 n-Butanol BRL BRL n-Propyl Alcohol 96.5 BRLsec-Butyl Alcohol BRL BRL t-Butyl Alcohol BRL BRL SW-846 8015M EthyleneGlycol 15229 1282 Glycols, mg/L Diethylene Glycol 22270 2937 TriethyleneGlycol 7112 2679 Tetraethylene glycol 5137 1648 SW-846 8260B Volatile1,2,4- 1.38 BRL Organic Compounds, Trimethylbenzene mg/L m- & p-Xylenes0.606 BRL MEK 19.9 53.6 Methyl Acetate 3.408 BRL Naphthalene 1.79 BRLo-Xylene 0.527 BRL Xylenes 1.133 BRL TX 1005 C₆-C₁₂ BRL BRL TotalPetroleum >C12-C28 22915 2351 Hydrocarbons, mg/L >C28-C35 BRL BRL TotalC6-C35 22915 2351 *BRL: Below Recordable Limits

Example 7 High Shear Butane Conversion

A run with conditions and equipment similar to Example 5 was conductedwith butane gas substituted for ethane. During this run, 1 L of waterwas injected into vessel 10 to assist in steam stripping of organicspresent. The analytical results are presented in Table 9.

TABLE 9 MBM 39-CW Cold Trap Liquid Test Method Component MBM 39-CWSW-846 8015D Non- 2-Propanol BRL* Purgeable Organic Ethanol 117Compounds, mg/L Isobutyl Alcohol BRL Methanol 276 n-Butanol BRL n-PropylAlcohol 24.0 sec-Butyl Alcohol BRL t-Butyl Alcohol BRL SW-846 8015MEthylene Glycol BRL Glycols, mg/L Diethylene Glycol BRL TriethyleneGlycol BRL Tetraethylene glycol BRL SW-846 8260B Volatile Ethyl Acetate18 Organic Compounds, Ethylbenzene 0.462 mg/L MEK 23.9 Methyl Acetate18.25 n-Butylbenzene 0.462 n-Propylbenzene 0.343 o-Xylene 0.331 Toluene0.755 Xylenes 0.331 TX 1005 C₆-C₁₂ BRL Total Petroleum >C12-C28 3525Hydrocarbons, mg/L >C28-C35 BRL Total C6-C35 3525 *BRL: Below RecordableLimits

Example 8 Reaction of Carbon Monoxide and Hydrogen Via High Shear Mixing

The following example demonstrates the ability of the high shear deviceto facilitate the reaction between carbon monoxide and hydrogen in asynthesis gas conversion operation similar to what is commonly known asthe Fischer Tropsch reaction where higher molecular weight hydrocarbonsare synthesized.

An external IKA MK 2000 mill 40 (Registered trademark of IKA Works, IncWilmington, N.C.) was connected to a 10 liter stirred reactor. Theapparatus used for the high shear process 400 for the reaction of CO andH₂ in this example is shown schematically in FIG. 4.

The ten liter reactor 10 was formed by welding a section of ten inchdiameter stainless steel pipe with a base plate and a head plateequipped with an agitator shaft and seal. Reactor 10 comprised internalpaddle agitator 110 and a cooling coil 125. Reactor 10 also comprisedpressure relief valve 17, discharge line 21, temperature probe 2 andpressure gauge 3. Heating mantle 120 was used to heat reactor 10 duringstart-up.

Reactor 10 was charged with eight liters of methanol (anhydrous, 99.8%)used as the carrier fluid and 5 grams of Triruthenium dodecacarbonyl(99%) catalyst, both supplied by Sigma-Aldrich Corporation, St. Louis,Mo.

Reactor 10 was sealed and purged with hydrogen. Circulation of catalystslurry was initiated with heating. The recirculating pump 5 was a RoperType 1 gear pump, Roper Pump Company (Commerce Ga.).

Dispersible gas stream comprising a mixed gas stream having an H₂:COmole ratio of 2 was fed via dispersible inlet line 22 into the inlet ofthe IKA unit 40 at ambient temperature, and gas flow was regulated bymeans of a pressure relief valve (not shown) between the supply manifold(not shown) and the reactor IKA unit 40. The reaction was then carriedout, maintaining the flow of mixed gases into the reactor. Pressures andtemperatures are tabulated in Table 10.

TABLE 10 Pressures and Temperatures for Example 8 Pump 5 Reactor 10Mixed Gas Time Pressure Pressure Temperature Flow (min) (psig) kPa(psig) kPa (° C.) (cc/min) 0 80 552 23 159 61 50 60 122 841 70 531 77 81120 162 1117 115 538 78 183 180 193 1331 154 545 79 200

Excess volatiles were vented through reactor 10 via condenser 130 whichwas cooled by water. Reactor 10 vent gas line 17 was used to vent excesshydrogen, CO and volatile reaction products. High shear device 40 wasset to 60 Hz. After 180 min the mixed gas flow in line 22 wasterminated, the pressure of reactor 10 was reduced, and high shearsystem 400 was allowed to cool to room temperature. A sample was drawnfrom reactor 10 and analyzed using gas chromatography. The results ofthe analysis are presented as Table 11.

TABLE 11 Gas Chromatograph Results from Example 8 Component Weight %Methanol 90.83 n-hexane* 4.63 3-Methylpentane 1.64 2,4-Dimethylpentane0.85 2-Methylpentane 0.66 C22 0.20 msc 1.19 Total 100.00 *Used as arinsing agent

The results indicate that the system produced several higher molecularweight (C5⁺) hydrocarbon reaction products.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Where numerical ranges or limitations are expressly stated, such expressranges or limitations should be understood to include iterative rangesor limitations of like magnitude falling within the expressly statedranges or limitations (e.g., from about 1 to about 10 includes, 2, 3, 4,etc.; greater than 0.10 includes 0.11, 0.12, 0.13, and so forth). Use ofthe term “optionally” with respect to any element of a claim is intendedto mean that the subject element is required, or alternatively, is notrequired. Both alternatives are intended to be within the scope of theclaim. Use of broader terms such as comprises, includes, having, etc.should be understood to provide support for narrower terms such asconsisting of, consisting essentially of, comprised substantially of,and the like.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference, to the extent theyprovide exemplary, procedural or other details supplementary to thoseset forth herein.

What is claimed is:
 1. A method of reacting one or more components in aliquid medium to form an organic product, the method comprising: feedinga carbonaceous gas and a liquid medium to a high shear device comprisingat least two generators, each generator comprising a toothed rotor and acomplementarily-shaped stator; processing the gas and the liquid mediumunder shearing conditions in the high shear device, resulting in anemulsion comprising at least some of the carbonaceous gas dispersed inthe liquid medium, wherein the dispersed carbonaceous gas comprises gasbubbles with a mean diameter of less than about 1 μm; and reacting theemulsion to produce the organic product.
 2. The method of claim 1,wherein the high shear device produces a local pressure of at leastabout 1034.2 MPa (150,000 psi) at the tip of a first rotor disposedtherein.
 3. The method of claim 2 wherein the organic product comprisesalkanes, olefins, aromatics, or combinations thereof.
 4. The method ofclaim 1, wherein the carbonaceous gas comprises carbon monoxide and thehydrogen-based liquid medium comprises methanol.
 5. The method of claim1, wherein the method further comprises feeding hydrogen to the highshear device, and wherein the organic product comprises ethanol.
 6. Themethod of claim 1 further comprising utilizing a catalyst to promote theformation of the organic product.
 7. The method of claim 6, wherein thecatalyst is a hydrogenation catalyst.
 8. The method of claim 6, whereinthe catalyst is a carbonylation catalyst.
 9. The method of claim 1,wherein the high shear device comprises at least one generatorcomprising a rotor and a stator separated by a shear gap therebetweenthat is in the range of from about 1 μm to about 3 mm.
 10. The method ofclaim 9, wherein shearing conditions comprises a localized temperatureat a tip of the first rotor of at least 500° C.
 11. A method ofproducing a liquid product comprising an organic, the method comprising:introducing gas and liquid carrier into a high shear device comprisingat least one toothed rotor and at least one complementarily-shapedstator; shearing contents of the high shear device at a shear rate of atleast 10,000 s⁻¹, resulting in an emulsion comprising at least some ofthe gas dispersed in the liquid carrier, wherein the dispersed gascomprises gas bubbles with a mean diameter of less than about 1 μm;reacting the emulsion to produce the liquid product; and recovering theliquid product.
 12. The method of claim 11, wherein the liquid productcomprises C2+ hydrocarbons, C2+ oxygenates, and combinations thereof.13. The method of claim 11, wherein the gas is selected from the groupconsisting of carbon dioxide, carbon monoxide, methane, ethane, propane,butane, pentane, methanol, and combinations thereof.
 14. The method ofclaim 11, wherein the gas comprises a hydrogen source, and wherein theorganic is one of alkanes, olefins, aromatics, or combinations thereof.